1,3,4(2H)‐Isoquinolinetriones: evaluation of amino‐substituted derivatives as redox mediator herbicides

Amino‐substituted derivatives of 2‐ethyl‐1,3,4(2H)‐isoquinolinetrione have been prepared with the aim of enhancing their hydrolytic stabilities relative to other isoquinolinetriones, and hence potentially improving their herbicidal effects. 5‐Amino‐2‐ethyl‐1,3,4(2H)‐isoquinolinetrione has been shown to be 12 and 8 times more stable towards hydrolysis than the isomeric 7‐ and 8‐amino derivatives, respectively, and 120 times more stable than 2‐ethyl‐1,3,4(2H)‐isoquinolinetrione itself. Pulse radiolysis studies have shown 5‐amino‐2‐ethyl‐1,3,4(2H)‐isoquinolinetrione to have free‐radical properties which could enhance the generation of superoxide radicals in plants. The compound is a potent stimulator of the light‐dependent consumption of oxygen at photosystem I in isolated chloroplasts and also shows high activity in isolated leaf discs. Evidence is presented which indicates that the rate of foliar uptake is a major factor affecting herbicidal activity for this compound. © 2000 Society of Chemical Industry     

The discovery of HNPC‐A3066: a novel strobilurin acaricide

BACKGROUND: Although more than ten strobilurin analogues have been commercialized since 1996 as fungicides, only one was available as an acaricide as of 2003. To search for novel strobilurin analogues with unique biological activities, a synthetic screening programme was carried out. RESULTS: Syntheses of compounds analogous to the commercialized fungicide metominostrobin and the acaricide fluacrypyrim led to the discovery of a lead compound, (E)‐2‐{2‐[[3,5‐bis(trifluoromethyl)phenoxy]methyl]phenyl}‐2‐(methoxyimino)‐N‐methylacetamide (3b), that showed moderate acaricidal activity against Tetranychus urticae Koch. Compound 3b has a 3,5‐(CF₃)₂‐phenoxymethyl group instead of the unsubstituted phenoxy substituent in metominostrobin. Optimization of compound 3b was achieved by introducing an oxime ether bridge along with an alkylthio(alkyl) branch in place of the oxymethylene chain between two aromatic moieties, as well as by replacing the methoxyiminoacetamide group with a methoxyacrylate structure, leading to (E)‐ methyl 2‐{2‐[[[(Z)[1‐(3,5‐bis(trifluoromethyl)phenyl)‐2‐methylthioethylidene]amino]oxy] methyl]phenyl}‐3‐methoxyacrylate (6c) and (E)‐ methyl 2‐{2‐[[[(Z)[1‐(3,5‐bis(trifluoromethyl)phenyl)‐1‐methylthiomethylidene]amino]oxy]methyl]phenyl}‐3‐methoxyacrylate (9a, HNPC‐A3066). CONCLUSION: The above two compounds (6c, 9a) were shown to exhibit potent acaricidal and fungicidal activity. Compound 9a (HNPC‐A3066) also exhibits larvicidal and ovicidal activities against various acarids. The acaricidal potency is comparable with those of commercial acaricides such as fluacrypyrim, tebufenpyrad and chlorfenapyr. Copyright © 2008 Society of Chemical Industry     

Increased foliar activity of clodinafop‐propargyl and/or tribenuron‐methyl by surfactants and their synergistic action on wild oat (Avena ludoviciana) and wild mustard (Sinapis arvensis)

Surfactants can improve postemergence herbicide efficacy and reduce the amount of herbicide required to obtain weed control. The effect of surfactants on the efficacy of herbicides is complicated and depends on the interaction among the plant, surfactant, and herbicide. The effects of surfactants on the efficacy of clodinafop‐propargyl and/or tribenuron‐methyl on wild oat (Avena ludoviciana) and wild mustard (Sinapis arvensis) under greenhouse conditions were investigated. In addition, the surface tension of aqueous solutions of the surfactants and surfactants + herbicides was determined. Significantly lower surface tension values were obtained with the aqueous solutions of citofrigate (Citogate plus Frigate) alone and with the herbicides used in this study. The citofrigate surfactant lead to the greatest enhancement of clodinafop‐propargyl and/or tribenuron‐methyl efficacy and the effect was species‐dependent. The efficacy of clodinafop‐propargyl and/or tribenuron‐methyl in the presence of surfactants in controlling wild oat was higher than for wild mustard. The foliar activity of the tested herbicides rose with increasing surfactant concentrations. The tank mixture of clodinafop‐propargyl and tribenuron‐methyl showed a synergistic effect in controlling wild oat and wild mustard. The synergistic effect in controlling wild mustard was greater than for wild oat.     

Resistance levels of sulfonylurea‐resistant Schoenoplectus juncoides (Roxb.) Palla with various Pro197 mutations in acetolactate synthase to imazosulfuron,bensulfuron‐methyl,metsulfuron‐methyl and imazaquin‐ammonium

An investigation, using herbicidal pot tests in a greenhouse condition, was conducted to determine the whole‐plant dose–response relationships to several acetolactate synthase (ALS)‐inhibiting herbicides of sulfonylurea (SU)‐resistant Schoenoplectus juncoides with various Pro₁₉₇ mutations in ALS that was collected from Japanese rice paddy fields. All the tested SU‐resistant accessions with a Pro₁₉₇ mutation were highly resistant to two commonly used SU herbicides (imazosulfuron and bensulfuron‐methyl), but were much less resistant to another SU herbicide, metsulfuron‐methyl, and were substantially not resistant to imazaquin‐ammonium. These cross‐resistance patterns have been known previously in fragments of S. juncoides and other weed species and were comprehensively confirmed in this study with a whole set of Pro₁₉₇ mutations. The analyses of resistance levels, based on ED₉₀ values, newly showed that different accessions with a common amino acid substitution in ALS1 showed similar responses to these herbicides (confirmed with four amino acid substitutions), that the rankings of resistance levels that were conferred by various Pro₁₉₇ mutations in ALS1 differed among the SU herbicides and that the resistance levels of the ALS2‐mutated accessions were higher than, lower than or similar to those of the corresponding ALS1‐mutated accessions, depending on the compared pair, but the deviation patterns were generally similar among the SU herbicides in each compared pair. The final finding might suggest that the abundance of ALS2 is not as stable as that of ALS1. In addition, as a result of these new findings, together with expected further research, a suggested possibility is that substituting amino acids at Pro₁₉₇ generally could be estimated by plotting each accession's ED₉₀ values of imazosulfuron and bensulfuron‐methyl in a two‐dimensional graph.     

The Ant Mosaic - Tropical Tree Crops and the Limiting of Pests and Diseases

Abstract

Field experiments were conducted to determine the effectiveness of herbicides in controlling Rottboellia cochinchinensis (Lour.) W. D. Clayton and Cyperus rotundus L. in upland rice (Oryza sativa L.) at different moisture regimes as imposed by a line source sprinkler system. Preemergence application of pendimethalin [N‐(1‐ethylpropyl)‐3,4‐dimethyl‐2,6‐dinitrobenzenamine] was highly effective in controlling R. cochinchinensis irrespective of soil moisture after herbicide application. Bentazon [3‐(1‐methylethyl)‐(1H)‐2,1,3‐benzothiadiazin‐4(3H)‐one 2,2‐dioxide] and 2,4‐D [(2,4‐dichlorophenoxy)acetic acid] applied at postemergence effectively controlled C. rotundus when moisture supply was well above pan evaporation. These herbicides also had no adverse effect on rice stand and resulted in higher yield over the control. Water application rates above upland pan evaporation for a season‐long period was essential to obtain a high response to weed control either by herbicides or hand weeding. The data suggest that proper weed control by herbicides or hand weeding will not result in high upland rice grain yields if moisture level from rains fall below the critical level.     

Involvement of cytochrome P‐450 enzyme activity in the selectivity and safening action of pyrazosulfuron‐ethyl

To investigate the selectivity and safening action of the sulfonylurea herbicide pyrazosulfuron‐ethyl (PSE), pyrazosulfuron‐ethyl O‐demethylase (PSEOD) activity involving oxidative metabolism by cytochrome P‐450 was studied in rice (Oryza sativa L cv Nipponbare) and Cyperus serotinus Rottb. Cytochrome P‐450‐dependent activity was demonstrated by the use of the inducers 1,8‐naphthalic anhydride and ethanol, the herbicides PSE, bensulfuron‐methyl, dimepiperate and dymron, or the inhibitor piperonyl butoxide (PBO). Growth inhibition in C serotinus seedlings was more severe than that in rice seedlings. O‐Dealkylation activities of PSE were induced differently in rice and in C serotinus, with distinctly higher activity in rice seedlings. The induced PSEOD activities were slightly inhibited by PBO in rice seedlings, whereas they were strongly inhibited in C serotinus seedlings. Dimepiperate and dymron were effective safeners of rice against PSE treatment. Treatments with herbicide alone resulted in less induction of PSEOD activity compared with combined treatments of the herbicide and safener. PSEOD activity in rice seedlings induced with herbicide alone was strongly inhibited by PBO, whereas it was weakly inhibited in rice seedlings induced with combinations of PSE and two safeners. These results suggest that O‐demethylation by cytochrome P‐450 enzymes may be involved in the metabolism of PSE and may contribute to its selectivity and safening action. Furthermore, these results suggest the existence of a multiple form of cytochrome P‐450 in plants. © 2001 Society of Chemical Industry     

Hydrolysis of triasulfuron,metsulfuron‐methyl and chlorsulfuron in alkaline soil and aqueous solutions

The hydrolysis of triasulfuron, metsulfuron‐methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH‐sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2–6.2) than under neutral and moderately alkaline conditions (8.2–9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo‐first‐order kinetics. There were no significant differences (P = 0.05) in the rate constants (k, day⁻¹) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the ‘rate constant’ on pH. The hydrolysis involving attack by neutral water was at least 100‐fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O‐demethylation of metsulfuron‐methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural alkaline soils. © 2000 Society of Chemical Industry     

Persistence and leaching of the herbicides acetochlor and terbuthylazine in an allophanic soil: comparisons of field results with PRZM‐3 predictions

Rates of degradation and adsorption of acetochlor [2‐chloro‐N‐ethoxymethyl‐6′‐ethylaceto‐o‐ toluidide] and terbuthylazine [N ²‐tert‐butyl‐6‐chloro‐N⁴‐ethyl‐1,3,5‐triazine‐2,4‐diamine] in a Horotiu sandy loam soil (Typic Orthic Allophanic) were determined under controlled temperature and soil moisture regimes. These were then combined with site‐specific soil properties and climatic conditions in the Pesticide Root Zone Model (PRZM‐3) to predict dissipation and leaching of the herbicides in the field. PRZM‐3 significantly under‐estimated dissipation of both herbicides in the field using parameters derived from the laboratory incubation studies. When these parameters were derived from the field trials, PRZM‐3 adequately predicted dissipation of both herbicides using a two‐rate dissipation sub‐model but under‐predicted the dissipation when a simpler single‐rate sub‐model was used. Earlier‐than‐expected appearance of both herbicides in sub‐soil layers were postulated to result from the non‐equilibrium adsorption/transport of the herbicides and preferential flow, which cannot be simulated by PRZM‐3. © 2000 Society of Chemical Industry     

The synthesis and fungicidal activity of derivatives of o- and p-Cyclohexylphenyl phosphorodichloridates and dichloridophosphorothioates

The synthesis of o- and p-cyclohexyphenyl phosphorodichloridates and dichloridophosphorothioates and their conversion into the corresponding dimethyl phosphates, phosphorodihydrazides, and phosphorodihydrazones, is discussed. o- and p-Cyclohexylphenyl N-phenylphosphoramidic chlorides were converted to the hydrazide and the O-methyl ester. The phosphorodichloridates were converted to the dihydrogen phosphates, but the dichloridophosphorothioates could not be hydrolysed in an analogous manner. Structure-activity relationships have been briefly discussed; the most active compound was o-cyclohexylphenyl O-methyl phosphoroisopropylidene hydrazone.     

An aspartate to glycine change in the carboxyl transferase domain of acetyl CoA carboxylase and non‐target‐site mechanism(s) confer resistance to ACCase inhibitor herbicides in a Lolium multiflorum population

BACKGROUND: The increasing use of ACCase‐inhibiting herbicides has resulted in evolved resistance in key grass weeds infesting cereal cropping systems worldwide. Here, a thorough and systematic approach is proposed to elucidate the basis of resistance to three ACCase herbicides in a Lolium multiflorum Lam. (Italian rye grass) population from the United Kingdom (UK24). RESULTS: Resistance to sethoxydim and pinoxaden was always associated with a dominant D2078G (Alopecurus myosuroides Huds. equivalent) target‐site mutation in UK24. Conversely, whole‐plant herbicide assays on predetermined ACCase genotypes showed very high levels of resistance to diclofop‐methyl for all three wild DD2078 and mutant DG2078 and GG2078 ACCase genotypes from the mixed resistant population UK24. This indicates the presence of other diclofop‐methyl‐specific resistance mechanism(s) yet to be determined in this population. The D2078G mutation could be detected using an unambiguous DNA‐based dCAPS procedure that proved very transferable to A. myosuroides, Avena fatua L., Setaria viridis (L.) Beauv. and Phalaris minor Retz. CONCLUSION: This study provides further understanding of the molecular basis of resistance to ACCase inhibitor herbicides in a Lolium population and a widely applicable PCR‐based method for monitoring the D2078G target‐site resistance mutation in five major grass weed species. Copyright © 2010 Society of Chemical Industry     

Removal of paraquat and atrazine from water by montmorillonite‐(Ce or Zr) phosphate cross‐linked compounds

The adsorption of paraquat (1,1′‐dimethyl‐4,4′‐bipyridilium dichloride) and atrazine (6‐chloro‐N ²‐ethyl‐N ⁴‐isopropyl‐1,3,5‐triazine‐2,4‐diamine) from aqueous solution onto two montmorillonite‐(Ce or Zr) phosphate cross‐linked compounds at different temperatures (288 K and 308 K) has been studied using batch experiments. The adsorption isotherms obtained for paraquat on both adsorbents may be classified as H‐type of the Giles classification, which suggests that paraquat molecules are strongly adsorbed on the samples. For the adsorption of atrazine, L‐type isotherms were obtained for both montmorillonite‐(Ce or Zr) phosphate compounds, which suggests that these compounds have a medium affinity for this herbicide. The increase in temperature from 288 K to 308 K did not have any clear effect on the adsorption process of paraquat on either adsorbent whereas atrazine adsorption decreased slightly as temperature increased, possibly due to a mainly physical process. Fourier transform infrared (FTIR) spectroscopic studies revealed that at the pH generated by the adsorbents, the cationic herbicide interacted to a greater extent with the negatively charged surface of the adsorbents than did atrazine. For both herbicides, the Ce‐montmorillonite adsorbent showed a higher adsorption capacity than the Zr‐montmorillonite adsorbent. © 2000 Society of Chemical Industry     

Synthesis and acaricidal activity of 4‐pyrimidinyloxy‐ and 4‐pyrimidinylaminoethylphenyl dioxolanes and oxime ethers

Novel types of mitochondrial respiration inhibitors at complex I, with emphasis on acaricidal activity, have been designed and prepared. The synthetic approach to these 4‐pyrimidinylphenyl ethyl ethers and amines with a specific ketal or oxime function in the phenyl side chain is outlined. Bioassays demonstrate their high potential against important spider mites, like Tetranychus urticae and Panonychus ulmi. Structure–activity relationship studies and several biological parameters are discussed. © 2000 Society of Chemical Industry     

7‐(4,6‐Dimethoxypyrimidinyl)oxy‐ and ‐thiophthalides as novel herbicides: Part 1. CGA 279 233: a new grass‐killer for rice

A series of novel types of 7‐(4,6‐dimethoxypyrimidin‐2‐yl)oxy ‐ and ‐thio‐3‐methyl‐1 (3H)‐isobenzofuranones were discovered at Dr R Maag AG. From the thio‐isobenzofuranyl series, CGA 279 233—BSI‐proposed common name pyriftalid—was chosen for further development as a grass herbicide for use in rice. General synthetic approaches to these new phthalic acid‐derived compounds are given, with emphasis on the synthesis of pyriftalid and its physico‐chemical behaviour. © 2001 Society of Chemical Industry     

Sensitivity of Botrytis cinerea to chitosan and acibenzolar‐S‐methyl

BACKGROUND: The antifungal properties of chitosan and acibenzolar‐S‐methyl were evaluated to assess their potential for protecting grapes against Botrytis cinerea Pers.: Fr. isolated from Vitis vinifera L. The objectives were to determine the effects of these compounds on the in vitro development of B. cinerea and to assess their effectiveness at controlling grey mould on grapes stored at different temperatures. RESULTS: Both agents significantly inhibited the radial growth of this fungus species. The EC₅₀ was 1.77 mg mL^?1 for chitosan and 3.44 mg mL^?1 for acibenzolar‐S‐methyl. In addition, single grapes treated with aqueous solutions of chitosan (1.0 and 2.5 mg mL^?1) and acibenzolar‐S‐methyl (1.0 and 3.0 mg mL^?1) were inoculated with B. cinerea and incubated at both 4 and 24 °C. After 4 days at 24 °C, all the concentrations of chitosan and acibenzolar‐S‐methyl significantly reduced B. cinerea growth. However, at 4 °C, significant differences were only observed between chitosan at 2.5 mg mL^?1 and acibenzolar‐S‐methyl at both 1.0 and 3.0 mg mL^?1 and the corresponding controls. After 3 days at 24 °C, the greatest reduction in lesion size was obtained in grapes pretreated with acibenzolar‐S‐methyl at 3.0 mg mL^?1. Only the highest doses of these products significantly reduced the lesion diameters when grapes were stored for 3 days at 4 °C. CONCLUSIONS: Chitosan and acibenzolar‐S‐methyl could directly inhibit the growth of Botrytis cinerea in vitro and confer resistance on grapes against grey mould. Pretreatment with these compounds could be an alternative to traditional fungicides in post‐harvest disease control in grapes. Copyright © 2010 Society of Chemical Industry     

Sensitivity of recently naturalised Digitaria spp. populations to 4‐hydroxyphenyl pyruvate dioxygenase‐ and acetolactate synthase‐inhibiting herbicides in maize

Until recently, Digitaria aequiglumis var. aequiglumis, native to South America, and Digitaria ciliaris subsp. nubica, native to Northeast Africa, were completely overlooked in Belgium due to their close morphological resemblance to Digitaria sanguinalis and Digitaria ischaemum. One of the possible reasons for their expansion in maize fields, besides for example the lack of crop rotation, might be a lower sensitivity to post‐emergence herbicides acting against panicoid grasses. Dose – response pot experiments were conducted in the glasshouse to evaluate the effectiveness of four foliar‐applied HPPD‐inhibiting herbicides (mesotrione, sulcotrione, tembotrione, topramezone) and two foliar‐applied ALS‐inhibiting herbicides (foramsulfuron, nicosulfuron) for controlling Belgian populations of D. aequiglumis and D. ciliaris subsp. Nubica, as well as local D. sanguinalis and D. ischaemum populations. In another dose–response pot experiment, the influence of growth stage at time of herbicide application on efficacy of topramezone and nicosulfuron for Digitaria spp. control was evaluated. In general, D. aequiglumis and D. ciliaris subsp. nubica populations were less sensitive to HPPD inhibitors than D. ischaemum and D. sanguinalis populations, except for D. aequiglumis treated with topramezone. Contrary to other herbicides tested, topramezone adequately controlled all D. aequiglumis populations at doses well below maximum authorised field dose. All species tested showed a progressive decrease in sensitivity to topramezone and nicosulfuron with seedling age. A satisfactory post‐emergence control of Digitaria species in the field will require appropriate choice of herbicide and dose, as well as more timely application.     

Multiple resistance across glufosinate,glyphosate, paraquat and ACCase‐inhibiting herbicides in an Eleusine indica population

An Eleusine indica population was previously reported as the first global case of field‐evolved glufosinate resistance. This study re‐examines glufosinate resistance and investigates multiple resistance to other herbicides in the population. Dose–response experiments with glufosinate showed that the resistant population is 5‐fold and 14‐fold resistant relative to the susceptible population, based on GR₅₀ and LD₅₀ R/S ratio respectively. The selected glufosinate‐resistant subpopulation also displayed a high‐level resistance to glyphosate, with the respective GR₅₀ and LD₅₀ R/S ratios being 12‐ and 144‐fold. In addition, the subpopulation also displayed a level of resistance to paraquat and ACCase‐inhibiting herbicides fluazifop‐P‐butyl, haloxyfop‐P‐methyl and butroxydim. ACCase gene sequencing revealed that the Trp‐2027‐Cys mutation is likely responsible for resistance to the ACCase inhibitors examined. Here, we confirm glufosinate resistance and importantly, we find very high‐level glyphosate resistance, as well as resistance to paraquat and ACCase‐inhibiting herbicides. This is the first confirmed report of a weed species that evolved multiple resistance across all the three non‐selective global herbicides, glufosinate, glyphosate and paraquat.     

Integrated management of Bromus diandrus in dryland cereal fields under no‐till

As herbicides have limited effect in controlling Bromus diandrus in no‐till dryland cereal fields, the integration of chemical and cultural methods needs to be investigated. A field study was carried out in Lleida (Spain) during 2008–09, 2009–10 and 2010–11 seasons, in a no‐till winter cereal field integrating delayed crop sowing with herbicides in a barley–wheat–wheat rotation. Three crop sowing dates were considered: D1, mid‐October; D2, mid‐November; and D3, early December, and the herbicides mesosulfuron‐methyl plus iodosulfuron‐methyl‐sodium were applied in wheat. Weed density, cumulative emergence and fecundity were estimated for each sowing date. In all three seasons, a significant reduction in the cumulative emergence of B. diandrus as compared to D1 was observed in D2 (82.0, 97.5 and 98.1%) and D3 (80.8, 98.7 and 97.2%). In addition, a significant decrease in weed density and seed rain was observed across all sowing dates and seasons. The herbicide used in wheat was more effective under delayed sowing, due to lower weed density and presence of less developed weed seedlings. After three seasons, the populations of B. diandrus were completely depleted in D2 and D3. This study demonstrates the possibility of eliminating brome infestations in dryland cereal fields in no‐till systems through the integration of cultural and chemical strategies.     

An integrated approach to control glyphosate‐resistant Ambrosia trifida with tillage and herbicides in glyphosate‐resistant maize

Glyphosate‐resistant Ambrosia trifida is a competitive and difficult‐to‐control annual broad‐leaved weed in several agronomic crops in the Midwestern United States and Ontario, Canada. The objectives of this study were to compare treatments for control of glyphosate‐resistant A. trifida with tillage followed by pre‐emergence (PRE) and/or post‐emergence (POST) herbicides in glyphosate‐resistant maize and to determine the impact of A. trifida escapes on maize yield. Field experiments were conducted in 2013 and 2014 in grower fields infested with glyphosate‐resistant A. trifida. Tillage prior to maize sowing resulted in 80–85% control compared with no tillage. Tillage followed by PRE application of saflufenacil plus dimethenamid‐P with or without atrazine resulted in 99% control compared with ≤86 and 96% control with PRE herbicides alone at 7 and 21 days after application respectively. Tillage or POST‐only herbicides resulted in 4–14 A. trifida plants m^?2, whereas a PRE and POST programme had <3 plants m^?2. Maize yield was greatest (13.1–14.2 tonnes ha^?1) with tillage followed by PRE and POST herbicide programme. The relationship between maize yield and late‐season density of A. trifida escapes showed a 50% maize yield reduction irrespective of control measures when A. trifida density was 8.4 plants m^?2. It was concluded that the combination of tillage with PRE and/or POST herbicides reduced A. trifida density and biomass accumulation early in the season and provided an integrated approach for effective management.     

Electrophysiological and behavioural responses of Pityophthorus pubescens (Coleoptera: Scolytinae) to (E,E)‐α‐farnesene, (R)‐(+)‐limonene and (S)‐(−)‐verbenone in Pinus radiata (Pinaceae) stands in northern Spain

BACKGROUND: Some twig beetles in the genus Pityophthorus (Coleoptera: Scolytinae) may vector pitch canker disease Fusarium circinatum (Niremberg & O'Donnell) of Pinus spp. (Pinaceae). Because Pityophthorus pubescens (Marsh.) has been found to be associated with F. circinatum in the Basque Country (northern Spain), various experiments were conducted to assess the beetle's behavioural responses to (E, E)‐α‐farnesene, (R)‐(+)‐limonene and (S)‐(?)‐verbenone to develop a potential inhibitor to host attraction. These experiments comprise electroantennographic and double‐choice olfactometer tests, as well as field assays in Pinus radiata D. Don stands. RESULTS: Both sexes of P. pubescens showed similar electroantennographic responses to different doses (from 1 ng to 1 µg in decadic steps) of each individual compound, with depolarisations to (S)‐(‐)‐verbenone (100 ng) being similar to those of the aggregation pheromone (+)‐trans‐pityol. In olfactometer assays, both sexes were significantly attracted to (+)‐trans‐pityol, but the attraction was reduced when increasing amounts of the chemicals were added to the pheromone. Particularly relevant was the repellent effect induced by (S)‐(?)‐verbenone at 1 ng dose and higher. In the field, (E, E)‐α‐farnesene, (R)‐(+)‐limonene and (S)‐(?)‐verbenone reduced significantly the number of beetles attracted to (+)‐trans‐pityol and racemic trans‐pityol, with (S)‐(?)‐verbenone being the most effective. CONCLUSIONS: (S)‐(?)‐Verbenone showed an interesting potential for use in the protection of P. radiata stands. A potentially effective strategy, which could be implemented in further, more in‐depth studies, could involve the use of this semiochemical as repellent and (+)‐trans‐pityol‐baited traps as attractant in a ‘push‐pull’ strategy. Copyright © 2012 Society of Chemical Industry     

Mechanisms of resistance to acetyl‐coenzyme A carboxylase‐inhibiting herbicides in a Hordeum leporinum population

A failure of acetyl‐coenzyme A carboxylase (ACCase)‐inhibiting herbicides to control a population of Hordeum leporinum Link (barleygrass) occurred following eight applications of these herbicides in both crops and pastures. This population was 7.6‐fold resistant to fluazifop‐P‐butyl compared with standard susceptible populations. The population was between 3.6‐ and 3.8‐fold resistant to other ACCase‐inhibiting herbicides, except butroxydim to which it was susceptible. ACCase extracted from resistant plants and assayed in the presence of herbicides in vitro was susceptible to fluazifop acid and other aryloxyphenoxypropanoate herbicides, but was 4‐fold less sensitive to sethoxydim compared with ACCase from susceptible plants. Resistant plants metabolised fluazifop acid about 1.3‐fold more rapidly compared with susceptible plants; however, sethoxydim was metabolised equally in both populations. Resistance to fluazifop‐P‐butyl and other aryloxyphenoxypropanoate herbicides may be the result of increased herbicide detoxification, whereas resistance to sethoxydim appears to be due to a modified target enzyme. Herbicide resistance in this population is unusual in that different mechanisms appear to confer resistance to the aryloxyphenoxypropanoate and cyclohexanedione herbicides. © 2000 Society of Chemical Industry