Vapor pressures of sulfonylurea herbicides

Vapor pressure values for agricultural chemicals are necessary for estimating volatilization and dissipation through transport in the vapor phase. The low vapor pressures of the sulfonylurea herbicides have presented significant challenges in vapor pressure determination. We have used the Knudsen gas effusion method at elevated temperatures and extrapolated to 25 °C. Along with the Knudsen method, computer calculations using the Grain equation were also used to estimate vapor pressure. The gas saturation method with quantitation by high performance liquid chromatography (HPLC) provided an upper limit that confirmed the low vapor pressures obtained using Knudsen gas effusion and computer calculations. We report the best available experimental results for the vapor pressures of sulfonylurea herbicides. © 2000 Society of Chemical Industry     

Joint action of sulfonylurea herbicides and MCPA

The joint action of mixtures of the sulfonylurea herbicides chlorsulfuron, metsulfuron and tribenuron and MCPA as a dimethylamine salt was assessed on Stellaria media L. and Lamium purpureum L. Two statistical analyses, and appropriate experimental designs, were used—the additive dose model (ADM) and the principle of parallel dose-response curves. The ADM analyses revealed that mixtures of the sulfony-lureas and MCPA were less potent than expected on Stellaria while the parallel-line assay analyses showed that activity of the sulfonylurea herbicides on Stellaria and Lamium was reduced in mixtures with MCPA. The antagonism was found to be dependent on the ratio of the two herbicides. Activity decreased with increasing MCPA ratios in the mixtures. Sequential spraying and selective placement of droplets revealed that MCPA only antagonized the sulfonylureas when the herbicides were in physical contact with each other. The benefits of applying both statistical methods when studying the joint action of two herbicides both possessing activity on the test plants are discussed. Action de melanges d'herbicides sulfonylurées et de MCPA L'action de melanges des herbicides sulfonylurées chlorsulfuron, metsulfuron et tribénuron avec le MCPA formulé en sel de diméthylamine, a été etudiée sur Stellaria media L. et Lamium purpureum L. Deux analyses statistiques asso-ciées a deux systèmes expérimentaux appropriés ont été utilisés: le modèle à doses additives (ADM) et le principe du parallélisme des cour-bes dose-effet. Les analyses ADM ont montré que les melanges de sulfonylurées et de MCPA ont été rnoins efficaces qu'attendu sur Stellaria. Les analyses en courbes parallèles ont montré que 1'activité des herbicides sulfonylurées sur Stellaria et Lamium était réduite dans des mélanges avec le MCPA.L'antagonisme dépendait du rapport entre les doses des deux herbicides, 1'activité décroissant avec 1'augmentation du taux de MCPA. Des traitements séquentiels et des dépôts localisés de gouttelettes ont montré que le MCPA n'était an-tagoniste des sulfonylurées que lorsque les herbicides étaient physiquement en contact. L'intérêt est discuté, d'utiliser les deux méthodes statistiques de concert pour étudier les interactions entre deux herbicides actifs sur les plantes test. Gemeinsame Wirkung von Sulfonylharnstoff-Herbiziden und MCPA Die Wirksamkeit von Mischungen der Sulfonyl-hamstoff-Herbizide Chlorsulfuron, Metsulfuron und Tribenuron mil MCPA als Dimethylamin-salz wurde an Stellaria media L. und Lamium purpureum L. bestimmt. Die Versuche wurden so angelegt, um 2 statistische Analysen anzuwen-den: das Additiv-Dosis-Modell (ADM) und das Prinzip paralleler Dosis-Wirkungs-Kurven. Die ADM-Analyse ergab, daß diese Mischungen gegenüber Stellaria weniger wirksam als erwartet waren, während die Parallel-Analyse zeigte, daß die Wirksamkeit der Sulfonylharnstoff-Herbiz-ide in Mischungen mil MCPA gegeniiber den beiden Arten herabgesetzt war. Es ergab sich, daß der Antagonismus vom Verhältnis der Mischungspartner abhängt. Die Wirkung nahm mit steigenden MCPA-Anteilen in den Mischungen ab. In Spritzfolgen und bei separater Applikation zeigte sich, daß MCPA nur dann gegenüber Sulfonylharnstoffe antagonistisch wirkte, wenn sich die Herbizide vermischten. Die Vorzüge der Anwendung der beiden statistischen Methoden zur Untersuchung des gemeinsamen Effektes von 2 Herbiziden ähnlicher Wirkung werden diskutiert.     

磺酰脲类除草剂对加拿大一枝黄花的防除效果

3月中旬至4月中旬加拿大一枝黄花幼苗高15cm以下，用75％甲嘧磺隆印～80g／667m^2或40％葫芦净150～200g／667m^2，防除非耕地加拿大一枝黄花的效果达90％以上，并能杀死根茎，可以达到一次用药根除的目的。     

磺酰脲类除草剂及其安全剂研究进展

本文简述了磺酰脲类除草剂的概况、长残留药害以及使用安全剂缓解残留药害的研究进展,并展望了磺酰脲类除草剂及其安全剂的发展前景。     

磺酰脲类除草剂加二甲四氯的除草效果

江苏省淮安市楚州区麦田杂草种类繁多 ,主要为禾本科杂草及阔叶杂草。阔叶杂草主要有猪殃殃、荠菜、牛繁缕、大巢菜等。前几年小麦田阔叶杂草的化学防除主要以冬前使用氯磺隆和甲磺隆 ,春后使用施甲合剂 ,防除效果比较理想。但随着氯磺隆和甲磺隆的限制使用 ,冬前的化除有一定难度。近年来除氯磺隆和甲磺隆以外的其它磺酰脲类除草剂如苄磺隆、噻磺隆、苯磺隆等防除麦田阔叶草具有较明显的防治效果 ,也比较经济 ,但防效表现慢 ,对大巢菜效果较差。为了筛选冬后麦田防除阔叶杂草高效、安全、经济的除草剂配方 ,我们进行了本试验1　材料与方法1…     

Cross-resistance pattern and alternative herbicides for Cyperus difformis resistant to sulfonylurea herbicides in Korea

A Cyperus difformis L accession from Chonnam province, Korea was tested for resistance to the sulfonylurea herbicide, imazosulfuron. The accession was confirmed to be resistant (R) and was cross-resistant to other sulfonylurea herbicides, bensulfuron-methyl, cyclosulfamuron and pyrazosulfuron-ethyl, the pyrimidinyl thiobenzoate herbicide, bispyribac-sodium, and the imidazolinone herbicide imazapyr, but not to imazaquin. Multiple resistance was tested using twelve herbicides with target sites other than acetolactate synthase (ALS). The R biotype could be controlled by other herbicides with different modes of action such as butachlor, carfentrazone-ethyl, clomeprop, dithiopyr, esprocarb, mefenacet, oxadiazon, pretilachlor, pyrazolate and thiobencarb, applied to soil at recommended rates. Several sulfonylurea herbicide-based mixtures can control both the R and S biotypes of C difformis, except sulfonylurea plus dimepiperate, molinate or pyriftalid, and pyrazolate plus butachlor. Although mixtures of sulfonylurea herbicides might be more effective, they should be avoided and used only in special cases. In terms of in vitro ALS activity, the R biotype was 1139-, 3583-, 1482-, 416-, 5- and 9-fold more resistant to bensulfuron-methyl, cyclosulfamuron, imazosulfuron, pyrazosulfuron-ethyl, bispyribac-sodium and imazapyr, respectively, than the S biotype. The in vivo ALS activity of the R biotype was also less affected by the sulfonylurea herbicides, imazosulfuron and pyrazosulfuron-ethyl, than the S biotype. Results of in vitro and in vivo ALS assays indicated that the resistance mechanism of C difformis to ALS inhibitor herbicides was primarily due to an alteration in the target enzyme, ALS. Greenhouse experiments showed delayed flowering and reduced seed production of the R biotype, which could possibly result in reduced fitness. This unusual observation needs to be confirmed in field situations.     

Orobanche aegyptiaca control in tomato fields with sulfonylurea herbicides

Field experiments were conducted from 1994 to 1997 at two locations to study the effectiveness of chlorsulfuron and triasulfuron applied through different irrigation methods (chemigation) for control of Orobanche aegyptiaca Pers. in tomato ( Lycopersicon esculentum Mill). Three split applications of chlorsulfuron at 2.5 g a.i. ha⁻¹ and of triasulfuron at 7.5 g a.i. ha⁻¹, through conventional sprinkler irrigation systems, 10–14 days apart followed immediately by sprinkling with water, controlled O. aegyptiaca by about 90% and 80% and increased crop yield 25–47% and 30%, respectively, without any crop injury symptoms. Repeated applications of the same herbicides at half rates resulted in slightly higher O. aegyptiaca control and crop yield than only one herbicide application at double rate. Chemigation by the sprinkler systems (microsprinklers, 60 m³ ha⁻¹) slightly increased the herbicide efficiency as compared with the high volume spray (800 m³ ha⁻¹). O. aegyptiaca control from sulfonylureas applied by drip chemigation was poor, as this probably requires very accurate timing and the herbicide distribution in the soil was not uniform.     

Computational analysis of mutated AHAS in response to sulfonylurea herbicides

Sulfonylurea (SU) herbicides that target acetohydroxyacid synthase (AHAS, also called acetolactate synthase (ALS)) are regarded as one of the most important classes of herbicides, due to their extremely low toxicity towards mammals, ultra‐low dosage application and high selectivity. However, mutations of AHAS to a herbicide‐insensitive form appear to be a worldwide problem for acquired resistance. In this study, three mutated AHAS sequences were used. In the mutated AHASs, the proline (Pro) was replaced by one of threonine (Thr), alanine (Ala) or serine (Ser) in AHAS amino acid (AA) position 197Pro. To understand the herbicide resistance mechanism, we built dimeric AHAS complex models based on 1YBH of protein data bank (PDB) with SU herbicide, chlorimuron ethyl (CIE), using a homology. The three mutated AHASs in complex with CIE were analysed, and the resistance mechanism to SU herbicides was studied by molecular dynamics (MD) simulation performed using GROMACS 4.5.5. MD simulation analysis of wild‐type and the three mutated dimeric AHAS–CIE complex systems revealed the conformational stability and changes in herbicide binding to dimeric AHAS system due to the mutation. Additionally, it showed that conformational change of amino acid residue 200Met (methionine) was associated with the imidazolinone herbicide resistance mechanism. According to our computation, the detailed mechanism of herbicide resistance was variable, depending on the type of mutated amino acid, providing new insights for designing herbicides specific to each mutant AHAS.     

Resistance of Rotala indica Koehne var. uliginosa Koehne to sulfonylurea herbicides

The present paper aims to quantify the degree of resistance development in Rotala indica Koehne var. uliginosa Koehne to sulfonylurea (SU) herbicides based on whole plant responses. Seeds of resistant (from Omagari City, Akita Prefecture, Japan) and susceptible (from Tsukuba City, Ibaraki Prefecture, Japan) R. indica plants were seeded in 200 cm² pots. The plants, at the 1.5 leaf stage, were blanket-applied with different rates of three sulfonylurea herbicides: bensulfuron methyl (BSM), pyrazosulfuron ethyl (PSE) and imazosulfuron (ISN). Of the three herbicides, the weed appears to have developed the highest degree of resistance to BSM. The resistant/susceptible (R/S) values based on mortality, root length and dry weight are consistently highest at 197, 157 and 101, respectively. Responses based on shoot length, however, showed a higher R/S value for PSE. Roots of R. indica are more sensitive to higher rates of SU herbicides than the shoots. Indeed, a high degree of resistance to SU herbicides have evolved in R. indica , for which the recommended field rates are not enough for effective control of the weed.     

Assessment of effects on non-target plants from sulfonylurea herbicides using field approaches

Since their introduction in the early 1980s, there have been a number of field studies conducted to assess the effects of sulfonylurea herbicides on non-target plants (i.e. plants not labeled for use). In these studies a wide variety of plant response assessment techniques have been used to measure effects on non-target plants. This paper examines the relationship of short-term plant response measurements to plant productivity measurements such as yield or quality. Whether short-term plant response measurements have a practical degree of accuracy and precision appropriate for hazard assessment on non-target plants from sulfonylureas is discussed. A comprehensive review of published literature and unpublished field studies of the effects of sulfonylureas on the yield and quality of non-target plant species is reported. When this information is coupled with exposure factors and environmental fate characteristics, the risks to non-target plants from sulfonylureas are similar to those from other herbicides used at higher application rates. © 1998 SCI.     

稻田杂草眼子菜对磺酰脲类除草剂的抗性研究

磺酰脲类除草剂在世界各地受到广泛应用,但其作用位点单一,杂草对其易产生抗药性.在贵州,磺酰脲类除草剂苄嘧磺隆、吡嘧磺隆应用至少有20年以上历史,为明确贵州稻田杂草眼子菜对磺酰脲类除草剂苄嘧磺隆、吡嘧磺隆的抗药性,指导农户合理用药,课题组采集贵州不同地区稻田杂草眼子菜鳞茎,采用《农药室内生物测定试验准则》的方法进行测定.试验结果表明:苄嘧磺隆、吡嘧磺隆对贵州稻田杂草眼子菜的防效较好,其鲜重防效在81％以上;所采样田块中眼子菜对苄嘧磺隆的IR值在1.00～7.53之间,对吡嘧磺隆的IR值在1.00～10.67之间.表明贵州稻田杂草眼子菜对磺酰脲类除草剂抗性水平不高,但部分田块已开始出现抗药性生态型眼子菜,且眼子菜对苄嘧磺隆、吡嘧磺隆两种药剂间存在着交互抗药性.     

Degradation of the sulfonylurea herbicides chlorsulfuron and triasulfuron in a high-organic-matter volcanic soil

The degradation rates of two sulfonylurea herbicides, chlorsulfuron and triasulfuron, were determined at two application rates, 15 and 30 g a.i. ha^–1, in a sandy loam soil of volcanic origin under controlled environment and field conditions. Residues were measured using a modified gas chromatographic (gc) determination method. Both herbicides degraded rapidly in the acidic soil (pH 5.7) with high organic matter levels (7.3% o.m.), generally according to first-order rate kinetics. The respective half-lives ranged from 22 to 38 d for chlorsulfuron and from 31 to 44 d for triasulfuron under five controlled temperature/soil moisture regimens, ranging from 10 to 30 °C and between 40% and 80% maximum water-holding capacity. Half-lives in the field were considerably shorter (13 d for chlorsulfuron and 12–13 d for triasulfuron). The degradation rates of the herbicides were influenced more by soil temperature than by soil moisture content. Bioassays using white mustard ( Sinapis alba L.) and forage sorghum [ Sorghum bicolor (L.) Moench] were also used to determine the persistence of phytotoxic residues of both herbicides in the field, and the results showed that the effects of chlorsulfuron disappeared within 8 weeks. Triasulfuron residues disappeared within 9 and 14 weeks for the 15 and 30 g a.i. ha^–1 rates respectively.     

A review of the activity,fate and mode of action of sulfonylurea herbicides

The sulfonylurea herbicides are a relatively new group of compounds which control broad-leaved weeds and some grasses in cereal crops. This literature review emphasises work reported on chlorsulfuron and met-sulfuron-methyl. The activity of the herbicides, their fate in soil and in plants, and their mode of action are discussed. In addition some of the methods of assaying these compounds are described.     

Mode of action,crop selectivity,and soil relations of the sulfonylurea herbicides

The sulfonylurea herbicides are characterized by broad-spectrum weed control at very low use rates (c. 2–75 g ha^?1), good crop selectivity, and very low acute and chronic animal toxicity. This class of herbicides acts through inhibition of acetolactate synthase (EC 4.1.3.18; also known as acetohydroxyacid synthase), thereby blocking the biosynthesis of the branched-chain amino acids valine, leucine and isoleucine. This inhibition leads to the rapid cessation of plant cell division and growth. Crop-selective sulfonylurea herbicides have been commercialized for use in wheat, barley, rice, corn, soybeans and oilseed rape, with additional crop-selective compounds in cotton, potatoes, and sugarbeet having been noted. Crop selectivity results from rapid metabolic inactivation of the herbicide in the tolerant crop. Under growth-room conditions, metabolic half-lives in tolerant crop plants range from 1–5 h, while sensitive plant species metabolize these herbicides much more slowly, with half-lives > 20 h. Pathways by which sulfonylurea herbicides are inactivated among these plants include aryl and aliphatic hydroxylation followed by glucose conjugation, sulfonylurea bridge hydrolysis and sulfonamide bond cleavage, oxidative O-demethylation and direct conjugation with (homo)glutathione. Sulfonylurea herbicides degrade in soil through a combination of bridge hydrolysis and microbial degradation. Hydrolysis is significantly faster under acidic (pH 5) than alkaline (pH 8) conditions, allowing the use of soil pH as a predictor of soil residual activity. Chemical and microbial processes combine to give typical field dissipation half-lives of 1–6 weeks, depending on the soil type, location and compound. Very short residual sulfonylurea herbicides with enhanced susceptibility to hydrolysis (DPX-L5300) and microbial degradation (thifensulfuron-methyl) have been developed.     

A bioassay method for formulation testing and residue studies of sulfonylurea and sulfonanylide herbicides

A bioassay method using the radicles of pea (Pisum sativum L.) and lupin (Lupinus angustifolius L.) was developed for the assessment of trials on herbicides of common use in the sulfonylurea class (chlorsulfuron, triasulfuron and metsulfuron-methyl) and in the sulfonanylide class (flumetsulam and metosulam). Soils within a range of pH 5.8–8.4 with textures from sand to clay were used in these experiments. The sensitivities of the species were similar in chlorsulfuron and flumetsulam trials and their response range varied with soil type and herbicide, e.g. between 0.75 and 6.0 ng triasulfuron g^?1 in the Wimmera grey clay and between 0.125 and 8.0 ng chlorsulfuron g^?1 soil in the Mallee sand. The method was demonstrated in a wide range of uses, encompassing tests of the initial bioactivity of formulations of chlorsulfuron and flumetsulam, monitoring the field leaching and persistence of triasulfuron and measuring relative potencies between the classes, using metsulfuron-methyl and metosulam. The bioassay response provided a high level of reproducibility and precision, which was measurable by the logistic curve-fitting procedure. In each case, R² values were >0.90 and lack-of-fit tests were clearly non-significant at the 0.05 level. Chi-square tests were used to measure differences between ED₅₀'s. The method does not require the pre-germination and selection of seedlings, daily watering or root-washing and results are obtained 7 days from sowing, providing favourable use for routine analyses and large-scale trials.     

A bioassay technique to study the leaching behaviour of sulfonylurea herbicides in different soils

A bioassay procedure is described for quantitative determination of sulfonylurea herbicides in water and for studying their leaching behaviour in soils. Sunflower (Helianthus annuus L.) was found a more susceptible bioassay species than turnip (Brassica rapa L.) or lentil (Lens culinaris Medic.). The limit of quantitative detection (EC₃₀) in soil leachates was 0.12 μg 1^?1 for triasulfuron and 0.15 μg 1^?1 for metsulfuron-methyl. Leaching experiments were carried out by uniformly packing the soil in glass columns corresponding to its natural bulk density and applying simulated irrigation of 50 mm day^?1 with leachate water from untreated soil columns. Results obtained by measuring fresh weights of the true leaves of sunflowers in soil leachates showed that metsulfuron-methyl was much more mobile than triasulfuron in two soils with different sorption capacity. The BBA soil with low sorptive capacity showed very little retardation of both herbicides in the columns. The Horotiu soil with high sorptive capacity retarded triasulfuron for a long period, even under high flow conditions. Une technique d'essai biologique pour étudier l'aptitu.de au lessivage des herbicides sul-fony-lurées dans des différents sols Un protocole d'essai biologique est décrit pour la détermination quantitative des herbicides sulfonylurées dans l'eau, et pour l'étude de leur lessivage dans les sols. Le tournesol (Helianthus annuus) a été reconnu comme une espèce pour l'essai biologique plus sensible que le navet (Brassica rapa) ou la lentille (Lens culinaris). La limite de détection quantitative (EC₃₀) dans le lessivat du sol a été 0,12 μg 1^?1 pour le triasulfuron et 0,15 μg 1^?1 pour le metsulfuron methyl. Des études de lessivage ont été con-duites en mettant unifomément du sol dans des colonnes de verre de façon équivalente à la densité naturelle dans le sol et en appliquant une irrigation simulée de 50 mm jour^?1 avec de l'eau d'un lessivat de sol non traité. Les résult ats obtenus en mesurant le poids frais des feuilles vraies de tournesol dans les lessivats de sol ont montré que le metsulfuron-methyl était beau-coup plus mobile que le triasulfuron dans les 2 sols de capacités d'adsorption différentes. Le sol BBA avec une capacité d'adsorption faible a entraiîné un faible ralentissement des 2 herbicides dans les colonnes. Le sol Horotiu avec une capacité d'adsorption élevée a retardé le triasulfuron pendant une longue période, même sous des conditions de fortes précipitations. Biotestmethode zur Bestimmung des Ein-waschungsverhaltens von Sulfonyl-Harnstoff-herbiziden in unterschiedlich sorptiven Böden Eine Biotestmethode zum quantitativen Nach-weis von Sulfonyl-Harnstoffherbiziden in Was-serproben zur Bestimmung des Einwaschungs-verhaltens wurde entwickelt. Sonnenblume (Helianthus annuus L.) war unter den geprüf-ten Testpflanzen wesentlich empfindlicher als Herbstrübe (Brassica rapa L.) oder Linse (Lens culinaris Medic.). Als empfindlichste Meßgröße erwiesen sich die Echten Laubblätter der Sonnenblume. Die Nachweisgrenzen (EC₃₀-Werte) in Bodenperkolatwasser lagen bei 0,12 μg 1^?1 für Triasulfuron und 0,15 μg l^?1 für Metsulf-uron-methyl. Die Einwaschungsversuche wurden in Glassäulen durchgeführt, wobei die Böden gleichmäßig entsprechend ihrer Lagerungsdichte gepackt wurden. Die Beregnung erfolgte mit 50 mm Perkolat/Tag, das von nicht mit Herbiziden behandelten Säulenversuchen vorab gewonnen wurde. In beiden, unterschiedlich sorptiven, Böden zeigte Met-sulfuron-methyl eine stärkere Einwaschung als Triasulfuron. Im schwach sorptiven BBA-Boden wurden beide Wirkstoffe kaum retardiert, während Triasulfuron im stark sorptiven Horotiu-Boden über einen langen Zeitraum, auch unter den extremen Flußraten, zurückgehalten wurde.     

Expression of a wheat cytochrome P450 monooxygenase cDNA in yeast catalyzes the metabolism of sulfonylurea herbicides

A wheat cytochrome P450 cDNA (CYP71C6v1) was cloned by RT-PCR and heterologously expressed in yeast. The microsomal fractions derived from this strain could catalyze the metabolism of some sulfonylurea herbicides such as chlorsulfuron, triasulfuron, metsulfuron-metyl, bensulfuron-metyl, and tribenuron-metyl, but not sulfonylurea herbicides such as thifensulfuron and pyrazosulfuron. Kinetic parameters K_m for chlorsulfuron and triasulfuron were 57 (±15) μM and 38 (±16) μM in vitro, respectively. Analysis of the metabolites demonstrated that the CYP71C6v1 functioned as a 5-phenyl ring hydroxylase when chlorsulfuron and triasulfuron were the substrates.     

磺酰脲类除草剂对抗、感性雨久花乙酰乳酸合成酶活性的影响

从2004年开始,延边地区稻田大量发生抗磺酰脲类除草剂苄嘧磺隆的抗药性生态型雨久花。为解析其抗药性突变机制,采用离体法测定了抗、感性雨久花乙酰乳酸合成酶活性。结果表明,抑制抗、感性雨久花乙酰乳酸合成酶活性50%的苄嘧磺隆剂量为253.44×10-7mol/L和2.80×10-7mol/L;抑制抗、感性雨久花乙酰乳酸合成酶活性50%的吡嘧磺隆剂量为1802.15×10-7mol/L和20.85×10-7mol/L。抗药性雨久花对苄嘧磺隆和吡嘧磺隆的抗性系数(RI50/SI50)值分别为90.6和86.5,并存在交互抗药性。确认抗药性突变系由其乙酰乳酸合成酶对磺酰脲类除草剂苄嘧磺隆、吡嘧磺隆反应钝化所致。