Discovery and structure optimization of a novel corn herbicide,tolpyralate

Tolpyralate, a new selective postemergence herbicide developed for the weed control in corn, possesses a unique chemical structure with a 1-alkoxyethyl methyl carbonate group on the N-ethyl pyrazole moiety. This compound shows high herbicidal activity against many weed species, including glyphosate-resistant Amaranthus tuberculatus. Tolpyralate targets 4-hydroxyphenylpyruvate dioxygenase (4-HPPD), which is involved in the tyrosine degradation pathway. Inhibition of the enzyme destroys the chlorophyll, thereby killing the susceptible weeds. Details of tolpyralate discovery, structure optimization, and biological activities are described.     

背负式静电喷雾器静电喷施对2种玉米田除草剂的减量效应

为了明确背负式静电喷雾器静电喷施对玉米田除草剂的减量效应,以土壤处理除草剂40%乙·莠SE和茎叶处理除草剂30%苯唑草酮SC+90%莠去津WG+专用助剂作为参试除草剂,测定了背负式静电喷雾器在不同施药剂量下的静电喷施效果。结果表明:背负式静电喷雾器静电喷施对40%乙·莠SE和30%苯唑草酮SC+90%莠去津WG+专用助剂均有明显的减量效应。当40%乙·莠SE和30%苯唑草酮SC+90%莠去津WG+专用助剂中90%莠去津WG的施用量分别降至2 850 mL/hm 2和825 g/hm 2时,较各自推荐施用量分别减少用药量36.67%和21.43%,对玉米田主要杂草仍有理想的控制效果,株防效超过64%,鲜重防效超过95%;并可最大限度地改善玉米茎、穗部性状,减轻对玉米产量的影响,较人工除草分别减产1.96%和0.29%。可见,背负式静电喷雾器在玉米田土壤处理除草剂和茎叶处理除草剂喷施中具有较大的应用价值。     

On the mechanism of selectivity of the corn herbicide BAS 662H: a combination of the novel auxin transport inhibitor diflufenzopyr and the auxin herbicide dicamba

BAS 662H, a 1:2.5 combination of the semicarbazone-type auxin transport inhibitor diflufenzopyr and the auxin herbicide dicamba, is used as a post-emergence herbicide in corn. The combination has been observed to provide more effective broadleaf weed control and improved tolerance in corn than typical rates of dicamba used alone. In order to analyze this phenomenon, the uptake, translocation, metabolism and action of both compounds, applied alone and in combination, were investigated in Amaranthus retroflexus L, Galium aparine L and corn (Zea mays L). When plants at the third-leaf stage were foliarly treated with diflufenzopyr and dicamba equivalent to field rates of 100 and 250 gha-1, respectively, diflufenzopyr synergistically increased dicamba-induced 1-aminocyclopropane-1-carboxylic acid (ACC) synthase activity and ethylene formation in G aparine and even more in A retroflexus, followed by accumulations of (+)-abscisic acid (ABA) in the shoot tissue within 20 h. This correlated with subsequent growth inhibition, hydrogen peroxide overproduction and progressive tissue damage. Diflufenzopyr also enhanced the activity of other auxin herbicides, such as quinclorac and picloram, and of the synthetic auxin, 1-naphthaleneacetic acid. After foliar and root application of [14C]diflufenzopyr, alone or as BAS 662H, considerably lower tissue concentrations and systemic translocation of radioactivity beyond treated plant parts were found in corn, compared to G aparine and particularly A retroflexus. Furthermore, diflufenzopyr decreased foliar uptake of [14C]dicamba by c 50% selectively in corn, compared to the treatment alone. Metabolism of [14C]diflufenzopyr was more rapid in corn than in the weed species. In combination, the two compounds had no mutual effect on their metabolic degradation. In BAS 662H, diflufenzopyr synergizes the herbicidal activity of dicamba in sensitive weed species. In corn this effect is prevented by a more rapid metabolism of diflufenzopyr, coupled with lower uptake and translocation. Selectivity of BAS 662H is additionally favoured by a higher crop tolerance to dicamba because of reduced foliar uptake of this herbicide in corn under the influence of diflufenzopyr.     

Protoporphyrinogen oxidase-inhibiting activity of the new,wheat-selective isoindoldione herbicide,cinidon-ethyl

Cinidon-ethyl (BAS 615H) is a new herbicide of isoindoldione structure which selectively controls a wide spectrum of broadleaf weeds in cereals. The uptake, translocation, metabolism and mode of action of cinidon-ethyl were investigated in Galium aparine L, Solanum nigrum L and the tolerant crop species wheat (Triticum aestivum L). When plants at the second-leaf stage were foliarly treated with cinidon-ethyl equivalent to a field rate of 50 g ha⁻¹ for 48 h, the light requirement for phytotoxicity and the symptoms of plant damage in the weed species, including rapid chlorophyll bleaching, desiccation and necrosis of the green tissues, were identical to those of inhibitors of porphyrin synthesis, such as acifluorfen-methyl. The selectivity of cinidon-ethyl between wheat and the weed species has been quantified as approximately 500-fold. Cinidon-ethyl strongly inhibited protoporphyrinogen oxidase (Protox) activity in vitro, with I₅₀ values of approximately 1 nM for the enzyme isolated from the weed species and from wheat. However, subsequent effects of herbicide action, with accumulation of protoporphyrin IX, light-dependent formation of 1-aminocyclopropane-1-carboxylic acid-derived ethylene, ethane evolution and desiccation of the green tissue, were induced by cinidon-ethyl only in the weed species. After foliar application of [¹⁴C] cinidon-ethyl, the herbicide, due to its lipophilic nature, was rapidly adsorbed by the epicuticular wax layer of the leaf surface before it penetrated into the leaf tissue more slowly. No significant differences between foliar and root absorption and translocation of the herbicide by S nigrum, G aparine and wheat were found. After foliar or root application of [¹⁴C]- cinidon-ethyl, translocation of ¹⁴C into untreated plant parts was minimal, as demonstrated by combustion analysis and autoradiography. Metabolism of [¹⁴C]cinidon-ethyl via its E-isomer and acid to further metabolites was more rapid in wheat than in S nigrum and G aparine. After 32 h of foliar treatment with 50 g ha⁻¹ of the [¹⁴C]-herbicide, approximately 47%, 36%, and 12% of the absorbed radioactivity, respectively, were found as unchanged parent or its biologically low active E-isomer and acid in the leaf tissue of G aparine, S nigrum and wheat. In conclusion, cinidon-ethyl is a Protox-inhibiting, peroxidizing herbicide which is effective through contact action in the green tissue of sensitive weed species. It is suggested that a more rapid metabolism, coupled with moderate leaf absorption, contribute to the tolerance of wheat to cinidon-ethyl. © 1999 Society of Chemical Industry     

Physiological effects of buthidazole on Zea mays L., Amaratithus retroflexus L., Medicago sativa L. and Agropyron repens(L.) Beauv.*

Buthidazole (3-[5-(1,1-dimethylethyl)-1,3.4-thiadiazol-2-yl]-4-hydroxy-l-methyl-2-imidazolidinone) at concentrations of 10^?6-10^?4M did not affect germination of corn (Zea mays L.,‘Pioneer 3780’), redroot pigweed (Amaranlhus retroflexus L.), alfalfa (Medicago saliva L., ‘Vernal’), and quackgrass (Agropyron repens(L.) Beauv.) seeds. Stressing the seeds obtained from mature corn plants treated either pre-emergence or pre- plant incorporated with buthidazole at several rates by accelerated ageing and cold treatments further indicated that this herbicide did not affect germination. Total photosynthesis and dark respiration of corn plants 12 days after pre-emergence application and of redroot pigweed, alfalfa, and quackgrass plants after postemergence application of buthidazole at several rates were measured with an infrared CO₂ analyser. The results suggested that buthidazole was a rapid inhibitor of photosynthesis of the sensitive redroot pigweed and quackgrass plants, with less effect on corn and alfalfa. Buthidazole did not affect respiration of the examined species except for a transitory increase in corn and alfalfa 12 days after pre-emergence or 4 h after postemergence treatment with buthidazole at 0.56 or 1.12 and 2.24 kg/ha, respectively. A long-term inhibition of quackgrass respiration 96 h after treatment with buthidazole at 1.12 and 224 kg/ha was also evident.     

Photosynthetic and growth responses of zea mays L and four weed species following post-emergence treatments with mesotrione and atrazinet

We compared photosynthesis and growth of Zea mays L (corn) and four weed species, Setaria viridis (L) Beauv (green foxtail), Echinochloa crus-galli (L) Beauv (barnyardgrass), Abutilon theophrasti Medic (velvetleaf), and Amaranthus retroflexus L (redroot pigweed), following foliar applications with atrazine, mesotrione, or a combination of atrazine and mesotrione in two greenhouse experiments. Plant responses to the three herbicide treatments were compared with responses of untreated plants (control). Photosynthesis on day 14 and dry mass of Z mays was not reduced by any of the herbicide treatments. Photosynthesis and dry mass of E crus-galli, A retroflexus and A theophrasti were significantly reduced by mesotrione and atrazine alone and in combination. Photosynthesis on day 14 and dry mass of large Sviridis plants were not suppressed by either herbicide applied alone. The mesotrione plus atrazine treatment was the most effective treatment for grass weed control because plants did not regain photosynthetic capacity and had significantly lower dry mass. Shoot dry mass of broadleaf weeds was significantly reduced by all three herbicide treatments, except for A retroflexus treated with mesotrione alone.     

Differential effect of diclofop-methyl on fatty acid biosynthesis in leaves of sensitive and tolerant plant species

The herbicide diclofop-methyl caused an early and pronounced inhibition of the incorporation of [¹⁴C]acetate into leaf lipids of the sensitive plant species maize (Zea may L.), wild oat (Avena fatua L.), and barnyardgrass (Echinochloa crus-galli L.). With an EC₅₀ value of approximately 10^?7M inhibition was already apparent 0.5–4 hr after herbicide application. The fatty acid biosynthesis of tolerant bean (Phaseolus vulgaris L.), sugar beet (Beta vulgaris L.), and soybean (Glycine max L.) was not affected, with one exception [wheat (Triticum aestivum L.) belongs to the more tolerant species]; the inhibition of fatty acid biosynthesis, however, was in the same order of magnitude as in sensitive plants. More detailed studies showed that in wheat a recovery from inhibition of fatty acid biosynthesis occurred. Four days after herbicide application (0.18 kg diclofop-methyl/ha) in wheat normal fatty acid biosynthesis was restored, whereas in sensitive maize a 60% inhibition was maintained over the whole experimental period (8 days). The results support the view that tolerance of wheat to diclofop-methyl is based on its inactivation in leaves, whereas the tolerance of dicotyledonous species may probably lie at the level of the site of action of diclofop-methyl. In experiments with intact leaves, the inhibition of fatty acid biosynthesis resulted in an enhanced flow of [¹⁴C]acetate into organic acids and amino acids. This effect, however, was not always reproducible in experiments with leaf pieces or isolated root tips.     

Use of corn root protoplasts in herbicide absorption studies

Intact and viable protoplasts were enzymatically isolated from corn (Zea mays L.) seedling roots and collected for herbicide absorption studies by differential centrifugation and flotation through a Ficoll density gradient. A method was developed for terminating herbicide absorption by rapid centrifugation of protoplasts out of solutions without washing the protoplasts. Within 10 sec, atrazine [2-chloro-4-ethylamino-6-isopropylamino-s-triazine] accumulated in protoplasts to a concentration 36% greater than the external concentration; no further absorption occurred through 30 min. However, 2,4-D [2,4-dichlorophenoxyacetic acid] accumulated to twice and 16 times the external concentration at pH 6.5 and 4.5, respectively. Calculations of theoretical 2,4-D concentrations in protoplasts also predicted greater accumulation at pH 4.5 than at pH 6.5. Both atrazine and 2,4-D absorption were consistent with previous measurements of absorption by plant tissues. Thus, corn root protoplasts are feasible experimental material for studying absorption of herbicides at the cellular level.     

Influence of the herbicides hexazinone and chlorsulfuron on the metabolism of isolated soybean leaf cells

The effects of the herbicides hexazinone [3-cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4(1H,3H)-dione] and chlorsulfuron (2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide) on the metabolism of enzymatically isolated leaf cells from soybean [Glycine max (L.) Merr., cv. ‘Essex’] were examined. Photosynthesis, protein, ribonucleic acid (RNA), and lipid syntheses were assayed by the incorporation of specific radioactive substrates into the isolated soybean leaf cells. These specific substrates were NaH¹⁴CO₃, [¹⁴C]leucine, [¹⁴C]uracil, and [¹⁴C]acetate, respectively. Time-course and concentration studies included incubation periods of 30, 60, and 120 min and concentrations of 0.1, 1, 10, and 100 μM of both herbicides. Photosynthesis was the most sensitive and first metabolic process inhibited by hexazinone. RNA and lipid syntheses were also inhibited significantly by hexazinone whereas the effect of this herbicide on protein synthesis was less. The most sensitive and first metabolic process inhibited by chlorsulfuron was lipid synthesis. Photosynthesis, RNA, and protein syntheses were affected significantly only by the highest concentration of this herbicide and longest exposure. Although these two herbicides may exert their herbicidal action by affecting other plant metabolic processes not examined in this study, hexazinone appears to be a strong photosynthetic inhibitor, while the herbicidal action of chlorsulfuron appeared to be related to its effects on lipid synthesis.     

河北省夏播玉米田杂草的发生及化学防除

本文论述了河北省夏播玉米田杂草群落的组成、翻耕和免耕两种不同种植方式的玉米田杂草的发生及消长规律 ,并就不同种植方式的玉米田提出了相应的化学防除药剂及施用技术 :在翻耕玉米田 ,以喷施乙阿合剂做播后苗前土壤处理为主 ;免耕贴茬玉米田 ,在作物播后苗前喷施农达混用乙阿合剂 ;麦垅套种的玉米田 ,在小麦收获后立即喷施玉农乐或玉农乐与阿特拉津混用做茎叶处理 ;采用克芜踪行间定向喷雾防除玉米生育后期的杂草     

烟嘧磺隆的微生物降解研究进展

烟嘧磺隆属磺酰脲类除草剂,因其对玉米安全,对一年生和多年生禾本科杂草及部分阔叶杂草、莎草科杂草高效而在玉米田广泛应用,但其在土壤中的残留则易对后茬敏感作物产生药害。微生物对烟嘧磺隆的降解有望成为修复污染土壤的有效措施。文章从烟嘧磺隆的使用及危害,可降解烟嘧磺隆的微生物种类及降解特性、降解途径、降解酶及其编码基因等方面进行了综述。目前有关烟嘧磺隆微生物降解的研究多集中于其降解菌的筛选、降解特性及降解途径等方面,对于其微生物降解过程中起关键作用的酶和基因方面的研究仍较少,因此未来的研究趋势将主要体现在降解复合菌系的培养、降解微生物的环境生态学、降解基因以及降解酶制剂等方面。     

A simulation of herbicide use based on weed spatial distribution

Intensive field surveys were conducted to deter mine the spatial distribution of composite broad leaf and grass weed seedlings in seven maize and five soybean fields in eastern Nebraska in 1992. Farmer fields where herbicides were applied in a 38-cm band over 76-cm spaced rows were chosen for this study. Weed populations were measured in the interrow and in the band-treated intrarow. Spatial maps constructed for grass or broadleaf weeds revealed that individual species as well as species assemblages are highly aggregated. On average, 30% of the sample area in the 12 fields surveyed was free of broadleaf weeds and 70% free of grass weeds in the interrow area (no her bicide). Where a pre-emergence herbicide was applied (intrarow), 71% of the sample area was free of broadleaf weeds and 94% free of grass weeds. Increasing the threshold to some value other than zero resulted in a larger field area not requiring a herbicide application. The results of these distribution studies indicate that herbicide use could be substantially reduced if weed dis tribution maps or real-time plant sensing were available to provide information for intermittent herbicide application systems or refinement of economic thresholds.     

The mode of action of chlorsulfuron: The lack of direct inhibition of plant DNA synthesis

Chlorsulfuron (2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzene-sulfonamide), the active ingredient in DuPont Glean Weed Killer, has been proposed to act by inhibiting plant cell division. In order to further define the mode of action of this new herbicide, studies were made of the effects of chlorsulfuron on processes associated with plant DNA synthesis. No inhibitory effects were observed on DNA synthesis in isolated plant nuclei, and the enzymes DNA polymerase and thymidine kinase. Nucleoside precursors of DNA were not effective in lessening chlorsulfuron inhibition of thymidine incorporation into DNA of corn root tips. These results indicate that chlorsulfuron does not inhibit plant cell division by a direct inhibition of DNA synthesis.     

植保无人机低容量喷雾防除玉米田杂草的雾滴沉积特性及除草效果

为探索植保无人机在4~6叶期玉米田喷施除草剂雾滴沉积分布规律及杂草防除效果, 通过改变药液雾滴粒径及喷液量测定了靶标杂草的雾滴沉积规律及对药效的影响?结果表明, 相同喷液量条件下, 靶区雾滴覆盖率和雾滴沉积量随雾滴粒径增大而增加, 雾滴密度随雾滴粒径增大而减少; 施药后30 d对杂草的株防效为72.87%~92.63%, 鲜重防效为83.07%~97.30%?研究结果为玉米田除草剂合理喷施?安全喷施提供了参考数据?     

Morphological and genetic variability of local Echinochloa accessions and the link with herbicide sensitivity

Echinochloa crus‐galli and Echinochloa muricata are common weeds in Belgian maize fields. Both species are morphologically difficult to distinguish and exhibit high morphological variability. Their response to herbicides varies from field to field. This study investigated whether the considerable morphological polymorphism found among Belgian Echinochloa accessions has a genetic background and whether it is consistently associated with differences in sensitivity to maize herbicides. For this purpose, accessions of E. crus‐galli and E. muricata were compared for morphological and genetic resemblance and tested for herbicide sensitivity. All accessions were planted in the field to examine the morphological traits. A cluster analysis was conducted to assess them for morphological diversity. DNA of leaf material was used for amplified fragment length polymorphism analysis to cluster the accessions genetically. Dose–response pot experiments were conducted in the glasshouse to assess the effectiveness of an acetolactate synthase (nicosulfuron), acetyl‐CoA carboxylase (cycloxydim) and 4‐hydroxyphenyl phosphate dioxygenase (topramezone) inhibiting herbicide. The genetic and morphological clusters were compared with the effective doses obtained from the dose–response bioassays. Morphological variation significantly correlated with genetic variation, but the relation with herbicide sensitivity was weak. Spikelet size and biomass characteristics are reliable discriminating characteristics for (sub)species classification. Intraspecies identification does not seem essential for optimisation of chemical control of E. crus‐galli and E. muricata in the field.     

Cytochrome P450‐mediated herbicide metabolism in plants: current understanding and prospects

Cytochrome P450s (P450s) have been at the center of herbicide metabolism research as a result of their ability to endow selectivity in crops and resistance in weeds. In the last 20 years, ≈30 P450s from diverse plant species have been revealed to possess herbicide‐metabolizing function, some of which were demonstrated to play a key role in plant herbicide sensitivity. Recent research even demonstrated that some P450s from crops and weeds metabolize numerous herbicides from various chemical backbones, which highlights the importance of P450s in the current agricultural systems. However, due to the enormous number of plant P450s and the complexity of their function, expression and regulation, it remains a challenge to fully explore the potential of P450‐mediated herbicide metabolism in crop improvement and herbicide resistance mitigation. Differences in the substrate specificity of each herbicide‐metabolizing P450 are now evident. Comparisons of the substrate specificity and protein structures of P450s will be beneficial for the discovery of selective herbicides and may lead to the development of crops with higher herbicide tolerance by transgenics or genome‐editing technologies. Furthermore, the knowledge will help design sound management strategies for weed resistance including the prediction of cross‐resistance patterns. Overcoming the ambiguity of P450 function in plant xenobiotic pathways will unlock the full potential of this enzyme family in advancing global agriculture and food security. © 2020 Society of Chemical Industry     

Inhibition of thiazopyr metabolism in plant seedlings by inhibitors of monooxygenases

Metabolism of the herbicide thiazopyr [methyl 2-(difluoromethyl)-5-(4, 5-dihydroO-lhiazo!vt)-4-(2-methylpropy!)-6-(trinuorornethyl)-3-pyridinecarboxy-late] was examined in young seedlings of redroot pigweed, grain sorghum, sunflower, corn and soybean. As previously observed with rat liver microsomes plants predominantly metabolized thiazopyr via oxidation reactions. Sulfur and carbon atoms in the thiazoline ring were the primary sites of plant oxygenases. De-esterification was also identified as an important pathway of transformations in plants. Although similar pathways of thiazopyr metabolism were observed among plants, our data indicated species differences in rates of thiazopyr degradation. Among species examined, pigweed (Amaranthus retroflexus L.) showed the fastest metabolism. Thiazopyr metabolism in pigweed was significantly inhibited by several cytochrome P450 monooxygenase inhibitors, among which tetcyclacis (TET) and piperonyl butoxide (PBO) were the most inhibitory. Thiazopyr metabolism in pigweed was not inhibited by organophosphates, known inhibitors of esterases. The results suggest that thiazopyr metabolism in plants is predominantly mediated via plant mono-oxygenases.     

Chlorophyll production and chloroplast development in norflurazon-treated plants

The chlorophyll production of wheat (Triticum vulgare L. cv. Mericopa), corn (Zea mays L. cv. Everta), and alfalfa (Medicago sativa L. cv. Saranac), treated with the herbicide 4-chloro-5-methylamino-2-(3-trifluoro-methylphenyl)pyridazin- 3-one (norflurazon) and grown under high light intensity (10 760 lux) was markedly reduced. Corn and wheat seedlings germinated and grown for 7 days in an agar medium containing 1 mg/1 norflurazon were almost completely bleached. Alfalfa was even more sensitive to norflurazon, 0.1 mg/1 causing almost complete chlorosis. Under low light intensity (10.76 lux) the influence of norflurazon on chlorophyll production was greatly reduced. It is thought that norflurazon inhibits carotenoid synthesis leaving the chlorophyll of the plant subject to photooxidation. Electron micrographs of chloroplasts from green, partially bleached, and bleached areas of corn leaves treated with norflurazon indicate that the herbicide causes progressive deterioration of the lamellar system.     

Soybean metabolism of chlorimuron ethyl: Physiological basis for soybean selectivity

Chlorimuron ethyl (2-([(4-chloro-6-methoxypyrimidine-2-yl)amino carbonyl]amino sulfonyl)benzoic acid, ethyl ester) is a highly active sulfonylurea herbicide for preemergence and postemergence use in soybeans. Excised soybean (Glycine max. cv. ‘Williams’) seedlings rapidly metabolized [¹⁴C]chlorimuron ethyl with a half-life of 1–3 hr. Common cocklebur (Xanthium pensylvancium Wallr.) and redroot pigweed (Amaranthus retroflexus L.), which are sensitive to chlorimuron ethyl, metabolized this herbicide much more slowly (half-life >30 hr). The major metabolite of chlorimuron ethyl in soybean seedlings is its homoglutathione conjugate, formed by displacement of the pyrimidinyl chlorine with the cysteine sulfhydryl group of homoglutathione. A minor metabolite is chlorimuron, the deesterified derivative of chlorimuron ethyl. Each of these metabolites is inactive against plant acetolactate synthase, the herbicidal target site of chlorimuron ethyl. Thus, soybean tolerance to chlorimuron ethyl results from its rapid metabolism in soybean seedlings to herbicidally inactive products.     

Studies on the mode of action of diflufenican in selected crop and weed species: Basis of selectivity of pre- and early post-emergence applications

Diflufenican, a pre- and early post-emergence herbicide, was found to be highly active against a wide range of weeds at application rates of 50–250 g ha-1. Studies on the mode of selectivity with [14C]diflufenican have demonstrated that selectivity between cereal crops and selected weed species is primarily due to differential uptake and indirectly to translocation; ‘depth protection’ appears to be the major reason for selectivity of soil-applied diflufenican.