Physiological activity spectra of existing graminicides and the new herbicide 2-(2-benzothiazolyl-oxy)-N-methyl-N-phenylacetamide (mefenacet)

inhibitory activities of existing graminicides on root regeneration from monocotyledonous (oat) and dicotyledonous (soybean) plant cuttings in the light, in the dark and on algal growth were compared with the respective inhibitory activities of the new herbicide 2-(2-benzothiazo-lyl-oxy)-N-methyl-N-phenylacetamide (mefenacet). The mefenacet activity spectrum resembled that of the α-chloroacetamide herbicides. Herbicide groups of other structure-activity can be distinguished by their distinct activity spectrum. The mono-oxygenase inhibitors piperonyl but-oxide (PBO) and 1-aminobenzotriazole (ABT) were found to antagonize the inhibitory activities of herbicides from the thiolcarbamate, α-chloroacetamide, and oxyacetic acid amide structure groups in the oat rooting and leaf growth tests. The critical evaluation of the presently available information on graminicide and safener mode of action suggests the concept that lipid biosynthesis on the physiological level and mono-oxygenase type enzymes on the biochemical level may hold the target sites for many of the graminicides and safeners discussed.     

HERBICIDES AS FERTILIZER ADDITIVES

Summary. Granulated compound fertilizers were tested as solid carriers for a variety of herbicides known to be active when applied as liquids.
Pasture and cereal experiments with 2,4-D and MCPA as fertilizer additives indicated considerable loss of herbicidal activity in comparison with spray formulations.
Residual herbicides such as TCA, propham and diuron retained their activity when added to fertilizer for application to root crops. The most effective of the herbicides used as fertilizer additives were TCA and propham, both of which gave good control of Avena fatua in sugar beet, and a mixture of chlorpropham and diuron gave promising results as a general weed control treatment in carrots.
It is concluded that the addition of these or similar herbicides to fertilizer granules may have advantages over conventional spray formulations for those crops which require broadcast pre-sowing applications of herbicides and fertilizer. For such crops the use of a granular fertilizer as the carrier instead of inert material could also have advantages over conventional granular herbicides, particularly by reducing transport and application costs.     

Comparison of physiological effects of fluazifop-butyl and sethoxydim on oat (Avena sativa L.)

Laboratory experiments were conducted to compare the physiological effects of two herbicides: fluazifop-butyl {butyl ( RS )-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]-propionate} and sethoxydim {(±)-2-[1-(ethoxyimino)butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one} on oat ( Avena sativa L. cv. Zenshin). The herbicides strongly inhibited growth of oat and induced chlorosis at the basal part of shoots and ethylene production from the seedlings. The phytotoxicity of these herbicides in oat seedlings was alleviated by 2,4-D (2,4-dichlorophenoxyacetic acid), but not by IAA (indole-3-acetic acid). Coleoptile elongation induced by 2,4-D or IAA was inhibited by fluazifop-butyl and sethoxydim, suggesting both herbicides possess the activity to inhibit this auxin action. Fluazifop (free acid) and sethoxydim inhibited proton excretion from oat roots but fluazifop-butyl did not. This proton excretion was not restored by 2,4-D or IAA. Furthermore, cellular electrolyte leakage in oat shoots was increased by both herbicides, indicating that the membrane permeability was increased. We conclude that fluazifop-butyl and sethoxydim may have the same mechanism of action which leads to disruption of membrane integrity, although fluazifop-butyl acts as a free acid after hydrolysis (fluazifop).     

10种除草剂对斜生栅藻的生长抑制活性研究

本文采用吸光度法测定了10个除草剂对斜生栅藻的生长抑制活性,其中包括3个原药和7个制剂产品,涉及12种有效成分。结果表明有5个药剂对斜生栅藻表现高毒,2个药剂为中等毒性,仅3个药剂为低毒。总体上磺酰脲类除草剂以及敌草隆、酰苯胺类吡唑草胺和吡氟酰草胺对斜生栅藻的毒性均较高。     

吡啶衍生物研究(IX):N-(1-甲氧羰基)乙基-N-[5-(2-氯吡啶-4-基)-1,3,4-噻二唑-2-基]酰胺的合成及除草活性

为了进一步研究前期发现的除草先导化合物2-仲丁氨基-5-(2-氯吡啶-4-基)-1，3，4-噻二唑(BCPT)的结构-活性关系并提高其除草活性，设计并合成了一系列N-(1-甲氧羰基)乙基-N-[5-(2-氯吡啶-4-基)-1，3，4-噻二唑-2-基]酰胺类化合物。其苗后除草活性测定结果表明，所有化合物的活性都远低于BCPT本身。说明BCPT可能具有与传统酰胺类除草剂不同的作用机制。     

1,3,4(2H)-isoquinolinetrione herbicides: Novel redox mediators of photosystem I

A series of 1,3,4(2H)-isoquinolinetriones have been found to be fast-acting post-emergence herbicides, producing symptoms of desiccation. These redox-active compounds are very potent stimulators of the light-dependent consumption of oxygen at photosystem I in isolated chloroplasts. Pulse radiolysis studies on 2-ethyl-1,3,4(2H)-isoquinolinetrione have shown it to have free-radical properties which could enhance the generation of superoxide radicals in plants. Electrochemical studies further support a redox mediator mode of action for the series. The compounds were found to be unstable towards hydrolysis, and this was considered to be a major factor limiting the overall herbicidal effects. Other parameters, related to uptake and/or translocation, which may limit the full expression of the herbicidal activity of certain compounds, are discussed.     

The relationship of metabolism studies to the modes of action of herbicides

Metabolism studies are necessary in the understanding of the mode of action of herbicides, their loss of activity and their selectivity. Molecular change of a herbicide may involve photochemical degradation, and non-enzymic or enzymic reactions that normally inactivate, but in some cases activate, a compound. Molecular change resulting in activation is discussed with regard to the (2,4-dichlorophenoxy)-alkanoic acids, the pyridines paraquat and diquat, the anilides benzoylprop-ethyl and flamprop-methyl, and the thiocarbamates. Inactivation due to metabolism is reviewed with regard to herbicides applied to soil and foliage. Of the soil-applied herbicides, the 1,3,5-triazines and the nitrile dichlobenil are exemplified as cases in which selectivity may be due largely to interspecific differences in metabolism. Of the foliage-applied translocated compounds, the metabolism of the phenoxyalkanoic acid herbicides has been extensively investigated and may involve conjugation, side-chain degradation or extension, ring hydroxylation and protein binding. The mode of action of glyphosate, asulam, dalapon and aminotriazole in perennial weeds is discussed with particular reference to their metabolism.     

Addition of a monovalent cationic pesticide to improve efficacy of bipyridyl herbicides in Hulah Valley soils

Bipyridyl herbicides are widely used in agriculture and gardening for non-selective weed control. Since they are toxic and relatively expensive, it is ecologically and economically desirable to reduce the amounts applied. A decrease in efficacy of these herbicides is caused by dust accumulated on leaves of weeds. This inactivation arises from the adsorption of the herbicides on dust particles, mainly made of clay minerals, lime and soil organic matter. In order to improve the efficacy and so lower the amounts applied, formulations were developed which include cationic pesticides approved for agricultural use, such as mepiquat or difenzoquat. Such addition restored the efficacy of the bipyridyl herbicides by reducing their binding to dust particles. The proposed formulations, which were tested on a number of different dust-covered plants, allowed the amounts of herbicide applied to be reduced to 50% of the minimum recommended rate. Neither mepiquat or difenzoquat had any herbicidal activity when sprayed alone at the added rates. The results suggest a procedure that may lower the required rates of contact herbicides, reducing costs and toxicity. This procedure, which can be applied immediately, may have broad implications in farming and gardening.     

Action of two herbicides on the microbial activity of soil cultivated with common bean (Phaseolus vulgaris) in conventional-till and no-till systems

The effects of application of the herbicides fluazifop‐p‐butyl and fomesafen and the commercial mixture of these herbicides on the microbial activity of a soil, cultivated with common bean under no‐till (NTS) and conventional‐till (CTS) systems, were evaluated. Microbial respiration was monitored for 63 days after application (DAA) of the herbicides, and the following evaluated at 12 and 51 DAA: microbial biomass carbon (MBC), microbial quotient (qMIC), metabolic quotient (qCO₂), percentage of bean root colonisation by mycorrhizal fungi and grain yield at the end of the cycle. A greater microbial respiratory rate was observed under NTS, with fluazifop‐p‐butyl providing the lowest respiration. At 12 DAA, MBC and qMIC were most affected negatively by fomesafen and by the commercial mixture of the two herbicides. Mycorrhizal colonisation was affected by the herbicides only at 12 DAA under CTS; however, in both periods, the highest value was found under NTS. All the herbicides caused a decrease in the MBC and qMIC values at 51 DAA; the qCO₂, which is related to the soil system stability, indicated a greater NTS balance over CTS. The herbicide fomesafen induced lower stability in the system. Lower grain yield was obtained without weed control (no herbicides) and with fomesafen‐only treatments, which may be attributed to the high weed infestation in the experimental area.     

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     

Recent developments in auxin biology and new opportunities for auxinic herbicide research

Auxinic herbicides mimic the effects of natural auxin. However, in spite of decades of research, the site(s) of action of auxinic herbicides has remained unknown and many physiological aspects of their function are unclear. Recent advances in auxin biology provide new opportunities for research into the mode of action of auxinic herbicides. Of considerable interest is the discovery of auxin receptors (TIR1 and possibly ABP1) that may lead to the discovery of auxinic herbicide site(s) of action. Knowledge of auxin-conjugating enzymes and auxin signal transduction components may shed new light on herbicide activity, selectivity in dicots, and mechanisms leading to phytotoxicity in sensitive plants. Analysis of genes induced in response to auxin may provide a novel approach for detection of off-target herbicide injury in crops. For example, the auxin-responsive gene GH3 is highly and specifically induced in response to auxinic herbicides in soybean, and may offer a novel method for diagnosing auxinic herbicide injury. Advances in our understanding of auxin biology will provide many new avenues and opportunities for auxinic herbicide research in the future.     

2-Benzyloxy-6,8-Dioxabicyclo[3.2.1]Octanes: New carbohydrate-derived herbicides

Structure—activity relationships in a new group of ‘cyclic ether’ herbicides have been probed by synthesis and evaluation of a range of isomers and analogues of 1,f-anhydro-4-O-benzyl-3-deoxy-2-O-methyl-β-D -gluco-pyranose. The absolute and relative stereochemical arrangement of the benzyloxy- and methoxy-groups and the pyran-ring oxygen atom possessed by this compound were essential for herbicidal activity, but the directionality of the —CH₂O— bridge unit was not. The benzyl substituent could be modified, especially by ortho-substitution on the benzene ring, without significant loss of herbicidal activity, but the azido-, ethoxy- and allyloxy-groups were the only replacements for the methoxy-group that did not result in a significant loss of potency. Selectivity for weeds in broad-leaf crops was enhanced by the introduction of an alkyl or substituted alkyl group at the anomeric carbon.     

Inhibition profile of trifludimoxazin towards PPO2 target site mutations

BACKGROUND

Target site resistance to herbicides that inhibit protoporphyrinogen IX oxidase (PPO; EC 1.3.3.4) has been described mainly in broadleaf weeds based on mutations in the gene designated protoporphyrinogen oxidase 2 (PPO2) and in one monocot weed species in protoporphyrinogen oxidase 1 (PPO1). To control PPO target site resistant weeds in future it is important to design new PPO-inhibiting herbicides that can control problematic weeds expressing mutant PPO enzymes. In this study, we assessed the efficacy of a new triazinone-type inhibitor, trifludimoxazin, to inhibit PPO2 enzymes carrying target site mutations in comparison with three widely used PPO-inhibiting herbicides.

RESULTS

Mutated Amaranthus spp. PPO2 enzymes were expressed in Escherichia coli, purified and measured biochemically for activity and inhibition kinetics, and used for complementation experiments in an E. coli hemG mutant that lacks the corresponding microbial PPO gene function. In addition, we used ectopic expression in Arabidopsis and structural PPO protein modeling to support the enzyme inhibition study. The generated data strongly suggest that trifludimoxazin is a strong inhibitor both at the enzyme level and in transgenics Arabidopsis ectopically expressing PPO2 target site mutations.

CONCLUSION

Trifludimoxazin is a potent PPO-inhibiting herbicide that inhibits various PPO2 enzymes carrying target site mutations and could be used as a chemical-based control strategy to mitigate the widespread occurrence of PPO target site resistance as well as weeds that have evolved resistance to other herbicide mode of actions. © 2022 BASF SE and The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Sulfonylurea herbicide-resistant Monochoria vaginalis in Korean rice culture

Nine Monochoria vaginalis Pres1 accessions from Chonnam province, Korea were tested for resistance to the sulfonylurea herbicide, imazosulfuron, in whole-plant response bioassay. All accessions were confirmed resistant (R) to imazosulfuron. The GR50 (imazosulfuron concentration that reduced shoot dry weight by 50%) values of R accessions were 1112-3172 (accession #9) times higher than that of the standard susceptible (S) accession. Accession #9 exhibited cross-resistance to other sulfonylurea herbicides, bensulfuron-methyl, cyclosulfamuron and pyrazosulfuron-ethyl, but not to the imidazolinone herbicides, imazapyr and imazaquin. The R biotype could be controlled by other herbicides with different modes of action, such as mefenacet and pyrazolate, applied to soil at recommended rates. Foliar-applied herbicides, 2,4-D and bentazone, also controlled both the R and S biotypes. Sulfonylurea-based mixtures, except ethoxysulfuron plus fentrazamide, did not control resistant M. vaginalis. Rice yield was reduced 70% by resistant M. vaginalis that escaped pyrazosulfuron-ethyl plus molinate, compared with hand weeding in direct-seeded rice culture. In contrast, rice yield was reduced 44% by resistant M. vaginalis that survived the pyrazosulfuron-ethyl plus molinate treatment, compared with pyrazolate plus butachlor in transplanted rice culture. In vitro acetolactate synthase (ALS) activity of the R biotype was 183, 35, 130 and 31 times more resistant to imazosulfuron, bensulfuron-methyl, cyclosulfamuron and pyrazosulfuron-ethyl, respectively, than the S biotype. Imidazolinone herbicides, imazapyr and imazaquin had similar effect on in vitro ALS activity of the R and S biotypes. The in vivo ALS activity of the R biotype was also less affected than the S biotype by the sulfonylurea herbicides imazosulfuron and pyrazosulfuron-ethyl. Results of in vitro and in vivo ALS assays indicate that the resistance mechanism of M. vaginalis to sulfonylurea herbicides may be due, in part, to an alteration in the target enzyme, ALS. Since the level of resistance in the enzyme assay was much lower than that in the whole-plant assay, other mechanisms of resistance, such as herbicide metabolism, may be involved.     

Imidazolinone inhibition of acetohydroxyacid synthase in vitro and in vivo

Imidazolinone herbicides inhibit the first enzyme of branched-chain amino acid biosynthesis, acetohydroxyacid synthase. The inhibition of the enzyme in vitro by these herbicides increases with incubation time, but is not irreversible, as deduced by reaction progress curves. In contrast to this result is the apparent irreversible inhibition of the enzyme by these imidazolinones that occurs when the herbicide is applied to intact corn plants. Plants treated with imidazolinone herbicide and then extracted showed dramatically reduced enzyme activity. This effect on extractable enzyme level occurred with several different imidazolinone herbicides in either foliar or soil application. The decrease in extractable enzyme activity could be observed within four hours after treatment. Herbicides other than imidazolinones did not reduce the extractable enzyme level. These findings suggest that the enzyme- imidazolinone interaction in vivo may be different from the interaction observed in vitro.     

Herbicide sorption to concrete and asphalt

In order to accurately predict the fate and behaviour of herbicides following application to hard surfaces, an understanding of the processes involved is required. Previous studies have demonstrated that herbicides with a low soil organic carbon partition coefficient (K(oc)) are preferentially removed from concrete and asphalt surfaces. It is possible, therefore, that sorption may play a role in retaining herbicides to hard surfaces. This study provides an indication of the extent to which herbicides may sorb to concrete and asphalt, and examines the results in the light of other research to identify the significance of sorption in describing herbicide losses after application. There was measurable sorption of herbicides to concrete and asphalt although this was limited compared with that to soils, especially for concrete. An exponential relationship between experimentally derived values of K(p) and literature values of K(oc) for asphalt was established (r(2) = 0.931); there was a weaker relationship for concrete (r(2) = 0.606). The experimentally derived K(p) values could be used to enhance the prediction of herbicide loss to receiving waters following application. It is probable that the fate of herbicides applied to concrete and asphalt surfaces depends more heavily on physical processes than is the case in soils.     

Action mechanisms of acetolactate synthase-inhibiting herbicides

Herbicides that target the acetolactate synthase (ALS) are among the most widely used weed control chemicals since their introduction into the marketplace in the early 1980s, including five classes (sulfonylureas, imidazolinones, triazolopyrimidines, pyrimidinylthio (or oxy)-benzoates and sulfonylamino-carbonyltriazolinones). The mechanism researches have progressed unprecedentedly in the last two decades. Primary mode of action of the ALS-inhibiting herbicides that interfere with the activity of ALS enzyme seems no longer in doubt. Three lines of investigation from physiology, genetics, molecular and chemical structure aspects came together to prove that ALS is the site of action. Researches on the effects of branched chain amino acids (BCAAs) synthesis or protein metabolism caused by ALS-inhibiting herbicide elicit lots of disputations. Besides these two main works, other secondary effects of ALS inhibition, such as buildup of 2-ketobutyrate (α-ketobutyrate or 2-KB) or 2-aminobutyrate (2-AB, the transamination product of 2-KB), depletion of intermediates of the pathway for some critical processes, disruption of photosynthesis transport and respiration system etc., have also been implicated in the mechanism of plant death. However, there are still some disputations and doubts on the precise mechanisms that need further probing into. Further more, as many ALS-inhibiting herbicides and their derivatives are chiral with one or even more enantiomers, which may behave quite differently in biochemical processes, the effects and the environmental fate of chiral herbicides need to be investigated stereospecifically. By this, we can have a better understanding about the herbicides and avoid unnecessary pollution load.     

磺酰脲类除草剂的降解机制及代谢产物的研究进展

磺酰脲类除草剂是一类高效,低毒和高选择性的除草剂,该类除草剂能有效防除阔叶杂草,其中有些品种对禾本科杂草也有一定的抑制作用。但同时因其用量低、对哺乳动物低毒以及独特的除草活性等特点而得到广泛应用。因此,了解磺酰脲类除草剂在土壤中的环境行为及归趋对于其科学合理使用、防止作物药害和保护农业生态环境具有非常重要的意义。根据笔者对磺酰脲类除草剂的深入研究,并总结归纳国内外的相关文献报道,对磺酰脲类除草剂的降解机制及其代谢产物的研究进行了综述,最后展望了磺酰脲类除草剂未来的发展趋势。     

Effect of the herbicides EPTC and linuron on cotton diseases caused by Rhizoctonia solani and Fusarium oxysporum f. sp. vasinfectum

The herbicides EPTC and linuron applied to soil in the field at three different concentrations X₂X, 1X, and 2X of recommended dose) decreased post-emergence, but not pre-emergence daraping-off in cotton incited by Rhizoctonia solani. Both herbicides at the two high concentrations significantly reduced wilt incited by Fusarium oxysporum f. sp. vasinfectum. Both herbicides reduced germination of chlamydospores of Fusarium in natural soil, but not in steamed soil. The 2X concentration of EPTC and linuron reduced the saprophytic activity of R. solani in soil. The effects of EPTC and linuron on post-emergence damping-off and wilt were attributed Ic their ability to suppress the saprophytic ability of R. solani and chlamydospore germinability of Fusarium in soil, respectively.     

Multiple effects of a naturally occurring proline to threonine substitution within acetolactate synthase in two herbicide-resistant populations of Lactuca serriola

Two populations of Lactuca serriola L. with resistance to acetolactate synthase (ALS)-inhibiting herbicides were discovered in wheat fields at two locations more than 25 km apart in South Australia. Both resistant populations carried a single base change within a highly conserved coding region of the ALS gene that coded for a single amino acid modification within ALS. The modification of proline 197 to threonine resulted in an enzyme that was highly resistant (>200-fold) to inhibition by sulfonylurea herbicides and moderately resistant to triazolopyrimidine and imidazolinone herbicides. The herbicide-resistant ALS was also less sensitive to inhibition by the branched-chain amino acids valine and leucine. In addition, the resistant enzyme had a lower K_m for pyruvate. However, extractable ALS activity was similar between resistant and susceptible plants. The substitution of threonine for proline 197 within ALS has multiple impacts on ALS enzyme activity in L. serriola that may influence the frequency of this resistant allele in the environment.