On the mode of action of the herbicides cinmethylin and 5-benzyloxymethyl-1, 2-isoxazolines: putative inhibitors of plant tyrosine aminotransferase

BACKGROUND: The mode of action of the grass herbicides cinmethylin and 5‐benzyloxymethyl‐1,2‐isoxazolines substituted with methylthiophene (methiozolin) or pyridine (ISO1, ISO2) was investigated. RESULTS: Physiological profiling using a series of biotests and metabolic profiling in treated duckweed (Lemna paucicostata L.) suggested a common mode of action for the herbicides. Symptoms of growth inhibition and photobleaching of new fronds in Lemna were accompanied with metabolite changes indicating an upregulation of shikimate and tyrosine metabolism, paralleled by decreased plastoquinone and carotenoid synthesis. Supplying Lemna with 10 µM of 4‐hydroxyphenylpyruvate (4‐HPP) reversed phytotoxic effects of cinmethylin and isoxazolines to a great extent, whereas the addition of L ‐tyrosine was ineffective. It was hypothesised that the herbicides block the conversion of tyrosine to 4‐HPP, catalysed by tyrosine aminotransferase (TAT), in the prenylquinone pathway which provides plastoquinone, a cofactor of phytoene desaturase in carotenoid synthesis. Accordingly, enhanced resistance to ISO1 treatment was observed in Arabidopsis thaliana L. mutants, which overexpress the yeast prephenate dehydrogenase in plastids as a TAT bypass. In addition, the herbicides were able to inhibit TAT7 activity in vitro for the recombinant enzyme of A. thaliana. CONCLUSION: The results suggest that TAT7 or another TAT isoenzyme is the putative target of the herbicides. Copyright © 2011 Society of Chemical Industry     

Protoporphyrinogen IX-oxidizing activities involved in the mode of action of a new compound N-[4-chloro-2-fluoro-5-{3-(2-fluorophenyl)-5-methyl-4,5-dihydroisoxazol-5-yl-methoxy}-phenyl]-3,4,5,6-tetrahydrophthalimide

N-[4-Chloro-2-fluoro-5-{3-(2-fluorophenyl)-5-methyl-4,5-dihydroisoxazol-5-yl-methoxy}-phenyl]-3,4,5,6-tetrahydrophthalimide (EK-5385) is an experimental substituted bicyclic herbicide. Soil-applied EK-5385 showed good rice selectivity and potent herbicidal activity on barnyardgrass (Echinochloa crus-galli var. oryzicola) at rates of 3.9-250 g a.i./ha. Barnyardgrass was exhibited normal growth under dark condition, however, the growth of shoot and root was severely inhibited under light condition (14/10 h of light/dark, 50 μmol/m²/s of photosynthetically active radiation) when treated with EK-5385, oxadiazon, and oxadiargyl. IC₅₀ of EK-5385 and oxadiargyl to chlorophyll loss in cucumber cotyledons was approximately 0.3 and 0.7 μM, respectively. IC₅₀ of EK-5385 and oxadiargyl to carotenoids loss in cucumber cotyledons was about 0.26 and 0.1 μM, respectively. IC₅₀ concentration of EK-5385 and oxadiargyl on Protox activity was approximately 5.5 and 8 nM, respectively. Cellular leakage occurred without lag period from cucumber leaf squares treated with 1 μM of EK-5385 and oxadiargyl under light exposure.     

1S,2R-((3-溴苯乙基) 氨基)-N-(4-氯-2-三氟甲基苯基) 环己烷基-1-磺酰胺对灰葡萄孢的抑菌活性及作用方式

研究了磺酰胺类化合物1S,2R-((3-溴苯乙基) 氨基)-N-(4-氯-2-三氟甲基苯基) 环己烷基-1-磺酰胺 (代号SYAUP-CN-26) 的抑菌活性及防治病害的作用方式。结果表明,SYAUP-CN-26可抑制多种植物病原真菌的菌丝生长和孢子萌发,尤以对灰葡萄孢Botrytis cinerea的抑制活性较强,EC₅₀值分别为1.82 μg/mL和14.98 μg/mL。20 μg/mL的SYAUP-CN-26处理能显著降低灰葡萄孢的产孢量、产菌核量,增加单菌核重。经该化合物处理过的灰葡萄孢孢子及菌丝致病力均降低。200 μg/mL的SYAUP-CN-26对番茄灰霉病的保护效果和治疗效果分别为83.11%和47.52%,保护作用优于治疗作用。     

Gas chromatographic determination of technical pyrazon (5-amino-4-chloro-2-phenyl-3(2H)pyridazinone)

5-Amino-4-chloro-2-phenyl-3(2H)pyridazinone (common name pyrazon) is the active ingredient of herbicide formulations known under the trade names Burex, Chlorazine, Pyramin, Phenazon. Pyrazon content was evaluated using the internal standard 4-chloro-5-methylamino-2-phenyl-3(2H)pyridazinone. FID detector and glass column (50 × 0.25 cm) packed with 2% cyclohexane-di-methanol succinate on silanised Chromosorb G (80-100 mesh) were used. Technical products can contain two interesting impurities, the non-active pyrazon isomer 4-amino-5-chloro-2-phenyI-3(2H)pyridazinone and the unreacted 4,5-dichloro-2-phenyl-3(2H)pyridazinone, the later of which issignificant from the point of view of toxicology. Determination of these two compounds under the conditions used for pyrazon is practically impossible. They were therefore determined on a separate glass column (70 × 0.24 cm) packed with 5% cyclohexane-di-methanol succinate on Chromosorb G (60-80 mesh). A standard addition method for small concentrations of 4,5-dichloro-2-phenyl-3(2H) pyridazinone in technical pyrazon products is also described.     

Selectivity and mode of action of flamprop-isopropyl,isopropyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido]propionate,in the control of Avena fatua in barley

The post-emergence herbicide isopropyl (±)-2-[N-(3-chloro-4-fluorophenyl)benzamido]propionate (flamprop-isopropyl) showed good activity against wild oat with selectivity in barley. The basis for activity and selectivity was similar to that previously established for benzoylprop-ethyl, and found to be dependent on its rate of degradation to the biologically active acid flamprop. Flamprop stunted the growth of the oat by inhibiting cell elongation and showed a relatively high rate of movement in the phloem, approximately five times that of benzoylprop. Selectivity of flamprop-isopropyl was dependent on its relative rate of hydrolysis and the subsequent detoxication of the acid to inactive conjugates. However, although the relative rate of de-esterification of flamprop-isopropyl was lower than that of benzoylprop-ethyl similar quantities of the parent ester gave comparable effects on oat. The inherent activity of flamprop is approximately twice that of benzoylprop. The effect of flamprop-isopropyl was best seen when the compound was applied during growth stages when the crop could offer the most effective competition to the wild oat. Throughout a range of growth stages the rate of hydrolysis of flamprop-isopropyl was higher in oat than in barley. The metabolism of the compound was not markedly affected when the plants were under stress.     

Phytotoxic sites of action for molecular design of modern herbicides (Part 2): Amino acid, lipid and cell wall biosynthesis, and other targets for future herbicides

A bird's eye review was tried in Part 2 of this series, 'Phytotoxic sites of action for molecular design of modern herbicides', in order to select the best selection of known and some novel plant-specific targets for molecular design of modern herbicides, which affect amino acid, lipid and cell wall biosynthesis. Although amino acid biosynthesis pathways, particularly those for aromatic amino acids, ammonia assimilation and branched amino acids, have been confirmed as reasonable herbicidal target domains, the other targets affecting plant growth more markedly than inhibition of 5-enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase and acetolactate synthase are discussed. In three essential enzymes involved in fatty acid biosynthesis in or in the vicinity of chloroplasts, acetyl-CoA carboxylase (ACCase), elongase(s) for very long chain fatty acids (VLCFA) and linolate monogalactosyldiacylglycerol desaturase, ACCase and elongase are more important targets for new herbicides. Although the effect of cellulose biosynthesis inhibitors is restricted to cell wall formation in growing plant cells only, there is a good chance to design the low-use rate herbicides also in this class of inhibitors. Other possible targets for new herbicides are also discussed.     

Chemical hydrolysis of 2-chloro-4,6-bis(alkylamino)-1,3,5-triazine herbicides and their breakdown in soil under the influence of adsorption

The determination of rate constants and the calculation of the activation parameters [activation energy (E_a), free energy of activation(ΔG^≠)and entropy of activation (ΔS^≠)] demonstrated the identity of the reaction kinetics of chemical hydrolysis of the chlorinated triazine herbicides simazine, atrazine, propazine and terbuthylazine. Persistence in soil could be estimated, from the hydrolytic half-life time, only in pH regions where these compounds were also sensitive to chemical hydrolysis. In general, the rate of hydrolysis increased in the presence of soil as the result of a catalysing effect of the soil in their breakdown. When half-lives in soil of these triazine herbicides were compared with adsorption constants, a functional relationship was observed in both soil types; as adsorption increased the half-life in soil also increased.     

Rhizome-induction activity of chiral 2-α-methylbenzylamino-4-alkylamino-6-chloro-1, 3, 5-triazines in Cyperus serotinus Rottb.

A cytokinin-like effect of chiral 2-α-methylbenzylamino-4-alkylamino-6-chloro-1,3,5-triazines was found using a rhizome-inducing assay with Cyperus serotinus Rottb. tubers. C. serotinus tubers germinated in distilled water yielded plantlets with roots and leaves. Secondary rhizomes were normally not observed within the regular 14-day incubation time in water culture, whereas after increasing incubation periods a very short rhizome appeared (controls). 6-Benzylaminopurine (BA) significantly stimulated rhizome induction, while other plant hormones were inactive. The (R)-isomers of the 1, 3, 5-triazine compounds also stimulated induction of the rhizomes, whereas the (S)-isomers did not. The described rhizome induction system seems to be suitable as a cytokinin bioassay. The (R)-1, 3, 5-triazine compounds showing rhizome-inducing activity (RI activity) inhibited root formation and plant growth at high concentrations with symptoms which were very similar to those of BA. Therefore, the (R)-isomers appear to act as cytokinins in the rhizome induction assay.     

Helicoverpa armigera preference and performance on three cultivars of short-duration pigeonpea (Cajanus cajan): the importance of whole plant assays

BACKGROUND

Helicoverpa armigera is a major pest of pigeonpea (Cajanus cajan). Efforts to develop pigeonpea varieties resistant to H. armigera attack have been met with limited success, despite reports of high levels of resistance to H. armigera in wild relatives of pigeonpea and reports of low to moderate levels of resistance in cultivated varieties. Here we examined H. armigera oviposition preference and larval performance on whole plants of three cultivars of short-duration pigeonpea: a susceptible control (ICPL 87) and two cultivars with purported host–plant resistance (ICPL 86012 and ICPL 88039).

RESULTS

In our no-choice oviposition experiment, H. armigera laid similar numbers of eggs on all three cultivars tested, but under choice conditions moths laid slightly more eggs on ICPL 88039. Larval growth and development were affected by cultivar, and larvae grew to the largest size (weight) and developed fastest on ICPL 86012. Moths laid most of their eggs on floral structures, sites where subsequent early instar larvae overwhelmingly fed. Experimentally placing neonate larvae at different locations on plants demonstrated that larvae placed on flowers experienced greater survival, faster development, and greater weight gain than those placed on leaves. The type and density of trichomes (a potential resistance trait) differed among cultivars and plant structures, but larvae selected to feed at sites where trichomes were absent.

CONCLUSION

Future work examining host–plant resistance against H. armigera should incorporate the behavioural preference of moths and larvae in experiments using whole plants as opposed to bioassays of excised plant parts in Petri dishes. © 2022 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Selectivity of SMY 1500 (4-amino-6-tert-butyl-3-ethylthio-l,2,4,triazin-5(4H)-one) in Triticum durum

Susceptibility to SMY 1500 (4-amino-6-tert-butyl-3-ethylthio-1.2.4-triazin-5(4H)-one) was studied in durum wheat (Triticum durum Desf.) cultivars in growth-chamber assays. Weight reduction, photosynthesis inhibition and herbicide levels were determined at various times after a 24-h herbicide treatment in two cultivars of durum wheat, one cultivar of spring wheat (Triticum aestivum L). and in the weed Bromus diandrus (Roth). Measurements of weight reduction distinguished between plants tolerant and plants susceptible to SMY 1500. Tolerant cultivars showed a lower herbicide content and photosynthesis inhibition than susceptible plants after the 24-h treatment. Thereafter, herbicide levels and photosystem II inhibition decreased faster in tolerant plants. Comparison with previous work showed that plants tolerated doses of SMY 1500 about four times higher than of its analogue, metribuzin. Herbicide content in leaves just after treatment, and rate of detoxification may explain the selectivity of SMY 1500 in these cereals.     

O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate,a new experimental insecticide and acaricide

The insecticidal and acaricidal action, anti-cholinesterase activity and toxicity to rats of a new experimental pesticide, O-ethyl O-isopropyl O-(5-methoxy-1-methyl-6-oxo-1H-pyridazin-4-yl) phosphorothioate ( I ), and those of some by-products found in the technical material, are described. High insecticidal and acaricidal effectiveness of I was found in laboratory and field trials. The activity as a soil insecticide in field trials was equal to, or greater than, that of other chemicals used at present.     

Degradation of the insecticide SD 8280, 2-chloro-1-(2, 4-dichlorophenyl)vinyl dimethyl phosphate,in soils

The degradation of the insecticide SD 8280 [2-chloro-1-(2,4-dichlorophenyl)vinyl dimethyl phosphate] in soil has been examined under laboratory conditions using two soils from rice-growing areas in Japan and one UK soil. In all soils SD 8280 underwent degradation to 1-(2,4-dichlorophenyl)ethanol, 2,4-dichlorobenzoic acid, 2-chloro-1-(2,4-dichlorophenyl)vinyl methyl hydrogen phosphate and 2′,4′-dichloro-acetophenone. These degradation products were present in the soils as free (extractable) compounds and as bound forms and soil binding occurred most extensively with 2,4-dichlorobenzoic acid. Polar products were also formed and these appeared to be in part the result of complexing of degradation products with the soil organic matter. The effect on the degradation of the insecticide of varying the moisture content of one soil was also examined. In soil incubated at 11, 17, 30 and 62% moisture the recovery of SD 8280 after 60 days was 71.0, 12.3, 9.0 and 11.3%, respectively. Although the rate of degradation varied, the same degradation products were detected in all samples.     

Photo-dimers from the photolysis of 2-dimethylamino-5, 6-dimethylpyrimidin-4-ol in aqueous solution

Photolysis of 2-dimethylamino-5, 6-dimethylpyrimidin-4-ol (I) in degassed aqueous solution yields two isomeric photo-dimers which are formed by dimerisation across the 5, 6-double bond of I. The yield of dimers is dependent upon the initial concentration of I and on the temperature; this can be explained in terms of a mechanism whereby pyrimidinol aggregates react to give dimers. The formation of aggregates can account for the fact that the quantum yield for the overall reaction of I was higher in degassed acetonitrile than in degassed aqueous solution, it can also account for four photo-dimers being formed in the former solvent and only two in the latter solvent. The photo-dimers revert to I when heated or on photolysis. That photodimers are not formed under natural conditions in the environment is considered to be partly because oxygen may react competitively with photo-excited pyrimidinol species and so prevent dimerisation.     

A biochemical mechanism for the conversion of thiophanate-methyl into methyl benzimidazol-2-YL carbamate (MBC) in plant tissue

Thin slices of potato tuber greatly accelerated the conversion of thiophanatemethyl into MBC. This was also observed when thiophanate-methyl was incubated with homogenates of apple, potato or with sap pressed from cucumber seedlings. Studies with cell-free extracts and crude enzyme preparations from potato tuber strongly suggested that in the presence of the enzyme polyphenol oxidase (EC 1.10.3.1) together with a suitable substrate, like DOPA or chlorogenic acid, the conversion of thiophanate-methyl into MBC is accelerated. Since it was found that some o- and p-quinones without polyphenol oxidase also could accelerate this conversion, it was concluded that unstable quinones generated by polyphenol oxidase from diphenol substrates might be the compounds which catalyze the formation of MBC from thiophanate-methyl.     

Effect of 4-amino-6-methyl-3-phenylamino-l,2,4-triazin-5(4H)-one on the lignification process catalysed by peroxidase from lupin (lupinus albus)

The molecular action of herbicides with a triazine structure, such as atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and metribuzin (4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5(4H)-one), has been related to their inhibition of the electron carrier system between chloroplastic photosystems II and I. This report provides evidence that 4-amino-6-methyl-3-phenylamino-1,2,4-triazin-5(4H)-one, a recently synthesised triazine, structurally analogous to metribuzin, causes a powerful inhibition of the cell-wall lignification catalysed by peroxidase from lupin. The two reactions involved in this lignification process are: oxidative polymerisation of coniferyl alcohol and the generation of hydrogen peroxide at the expense of NADH oxidation.     

The action of (S)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (1 R)-trans-chrysanthemate, (S)-bioallethrin,on single neurones in the central nervous system of the leech,Hirudo medicinalis

Intracellular recordings from identifiable neurones in the leech segmental ganglion in high (20 mM) magnesium Ringer solution showed that (S)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (1 R)-trans-chrysanthemate, (S)-bioallethrin, induced three phases of activity: (1) hyperexcitability; (2) repeated depolarisations accompanied by trains of action potentials; and (3) block of action potentials. A linear relation between log (time to onset) of both depolarisations and block and the log (applied dose) was observed over the range 3.44 × 10^?7–1.10 × 10^?3M. (S)-Bioallethrin was toxic to leeches at similar concentrations to those effective on isolated ganglia. The possible role of repeated depolarisations in the poisoning process is discussed.     

Titres of precocene ii (6, 7-dimethoxy-2, 2- dimethylchromene) and its metabolites in the haemolymph of larvae of the african armyworm Spodoptera exempta (walker) following topical treatment with the compound

No precocious metamorphosis or other morphogenetic effects were seen following topical treatment of fifth instar Spodoptera exempta with pre- cocene II. [3H]-Precocene II penetrated the larvae rapidly following topical application. An uptake of 47% was recorded in the first hour and an average of 27% for the first 3 h. Radioactivity in the haemolymph reached a maximum 4 h after treatment at 6–8% of the applied dose. A maximum titre of precocene of 1.1 × 10^?4 _M was observed 2 h after treatment and a biological half-life of around 1 h was recorded for the first 6 h. The metabolite precocene 11–3, 4-dihydrodiol appeared in the haemolymph with a maximum titre of 1.1 × 10^?4 _M at 4 h suggesting metabolism via the 3, 4-epoxide. At the same time an unidentified metabolite was observed possibly corresponding to the 6- and 7-(O)-desmethylated products described by others. Very large quantities of highly polar materials were observed in the haemolymph throughout the experiment and it is thought that these corresponded to conjugates. The evidence suggests that peripheral detoxication mechanisms do not operate sufficiently rapidly to prevent the establishment of a high titre of precocene. This, however, did not affect the corpora allata in this insect, whereas in a sensitive species that has been studied by other workers, necrosis of the glands would have resulted. Alternative explanations for insensitivity are discussed.     

N-苯基-2-(4,6-二甲氧基-2-嘧啶氧基)-6-氯-苄胺(ZJ1835)的除草活性研究

为明确新化合物N-苯基-2-(4,6-二甲氧基-2-嘧啶氧基)-6-氯-苄胺(ZJ1835)在棉花田的应用前景,就其对棉花的安全性、选择性、杀草谱和田间应用技术进行了研究。室内生物测定结果表明,ZJ1835对棉花生长初期有一定矮化作用,但不影响出苗和后期生长,在有效剂量225 g/hm2下对棉花安全性好;对不同棉花品种之间的安全性有一定差异,其中对王岳9913的安全性最好,其次为银山1号和福棉6号,对冀丰197安全性略差;该化合物在棉花与马唐、反枝苋之间的选择性系数分别为2.14和13.00,具有较好的选择性;多数田间常见杂草对其敏感,杀草谱较广。田间试验结果显示,ZJ1835在90～120 g/hm2有效剂量下对供试棉花安全性好,对棉田杂草总防效为82.1%～92.8%,具有一定的开发应用潜力。     

The basis of selectivity of 4-(2, 6-dichlorobenzyloxymethyl)-4-ethyl-2, 2-dimethyl-1, 3-dioxolan (WL 29, 226), a new pre-emergence herbicide for use in cereals

A series of pot experiments were undertaken to assess the selectivity of the pre-emergence herbicide 4-(2, 6-dichlorobenzyloxymethyl)-4-ethyl-2, 2, -dimethyl-1, 3-dioxolan (WL 29,226) against a number of annual weeds in wheat. When applied at dose rates of 0.5–2 kg/ha it gave good control of a number of annual monocotyledonous weeds, including Alopecurus myosuroides (blackgrass), without any adverse effects on the crop. WL 29,226 is relatively immobile in soil, remaining at the soil surface and thus favouring uptake via the emerging shoot. Since WL 29,226 is transported predominantly via the xylem, to reach its site of action in the regions of cell division, and hence to be effective, the compound has to penetrate the shoot either at or below the stem apex. The roots are inhibited only when these come into direct contact with the compound. Selectivity of the herbicide is dependent upon the relative anatomical positions of the stem apices of the weeds and the crop with respect to the soil surface. Mesocotyl elongation in many of the weed species was such that the meristematic tissue was raised to the soil surface and into contact with the compound during the emergence of the shoot. In contrast, the stem apex of wheat remained some distance below the soil surface until considerably later, by which time the leaf sheaths offered protection to the meristematic tissue from direct contact with the herbicide. Selectivity is further enhanced in the field as a result of both the depth of planting for wheat and the tendency of many annual weed species to germinate more readily when near the soil surface. Tolerance of the wheat is lost where it germinates in direct contact with the herbicide, due to the lack of any biochemical selectivity. Under field conditions WL 29,226 gives good control of many dicotyledonous species. In pot experiments, however, these exhibit some tolerance to the compound. Radio-tracer studies indicate that the tolerance shown by the shoots of these plants is due to limited transport of the herbicide from the shoot to its site of action at the apex. This suggests that control of broad-leaved weeds occurs predominantly through an inhibition of root growth. However, in species such as sugar-beet, soyabean and cotton a rapid rate of root elongation confers increased tolerance to the compound. Availability of WL 29,226 for uptake by young seedlings is favoured by soil moisture. Low temperatures further improve performance by reducing the rate of shoot emergence and hence prolonging contact with the compound at the most sensitive stage of growth. After emergence uptake of the compound via the shoot becomes a less efficient mode of entry.