Enhancement of superoxide production in vitro by the diphenyl ether herbicide nitrofen

Light-dependent reduction of p-nitro blue tetrazolium chloride (NBT) and 2,6-dichlorophenol-indophenol (DCPIP) was stimulated by nitrofen (2,4-dichlorophenyl p-nitrophenyl ether) in the presence or absence of the photosensitizer riboflavin. Enhancement of NBT reduction occurred at a concentration as low as 17 μM nitrofen. Nitrofen had no effect on dark reduction of NBT by dithionite, ascorbate, or reduced phenazine methosulfate. NBT reduction proceeded in solution saturated with either air or nitrogen. Stimulation by nitrofen in the presence or absence of riboflavin also occurred independently of oxygen. Superoxide dismutase (superoxide:superoxide oxidoreductase; EC 1.15.1.1) inhibited light-dependent, aerobic reduction of NBT and DCPIP with and without riboflavin. The nitrogen-stimulated component was also eliminated. Thus, it appears nitrofen can effect reduction of NBT (and DCPIP) anaerobically by transferring electrons directly to NBT (and DCPIP) through an oxygen-independent mechanism or aerobically via superoxide radicals.     

Development of tolerance to the diphenyl ether herbicide acifluorfen-methyl in excised cucumber (Cucumis sativus L.) cotyledons

Etiolated cucumber (Cucumis sativus L.) cotyledons and cotyledons greened for 24 hr in low light (75 μE m⁻² sec⁻¹; measured as PAR, i.e., photosynthetically active radiation between 400 and 700 nm) were susceptible to 1 μM acifluorfen-methyl (AFM), methyl-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, following an 8-hr exposure to high light (600 μE m⁻² sec⁻¹; PAR). Cotyledons greened in low light for 48 hr prior to treatment with 1 μM AFM in high light were tolerant. Injury was detected by monitoring efflux of 3-O-methyl-[¹⁴C]glucose from treated cotyledons excised from 6- or 7-day-old dark-grown seedlings. Although development of tolerance was light dependent, tolerance was not related specifically to seedling age. Tolerance to AFM injury was overcome partially by rubbing the adaxial surface of the leaf (i.e., the side of the cotyledon exposed to herbicide) with a wetted finger and was eliminated completely following abrasion with carborundum. Cuticle abrasion resulted in an increase in [¹⁴C]AFM uptake. Scanning electron microscopy revealed that abrasion resulted in disruption of the leaf surface. These induced aberrations in surface structure facilitated enhanced absorption of AFM. Nonpolar hydrocarbon constituents of cuticular and epicuticular waxes of 24- and 48-hr-greened cotyledons were examined using gas chromatography. There were no differences in these cuticular components. Transmission electron micrographs indicated there were also no differences in cuticle thickness. The light-dependent development of tolerance to AFM activity was due in part to a decrease in herbicide absorption. The mechanism(s) responsible for inhibition of herbicide uptake and tolerance are unknown.     

微生物降解二苯醚类除草剂的研究进展

本文概述了降解二苯醚类除草剂的微生物种类、降解机理及影响微生物降解二苯醚类除草剂的因素,指出利用微生物修复土壤中二苯醚类除草剂残留是一个有效的手段; 同时指出二苯醚类除草剂微生物降解过程中起关键作用的酶及基因有待于进一步研究。     

Nitro free radical formation of diphenyl ether herbicides is not necessary for their toxic action

The diphenyl ether herbicides MC 15608 {5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chloromethylbenzoate} and MC 10878 {5-[2-chloro-4-(trifluoromethyl)phenoxy]methyl benzoate} are structurally similar to acifluorfen-methyl (methyl ester of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-nitrobenzoic acid), except that the NO₂ is replaced by a Cl and H, respectively. These diphenyl ether herbicides required light for herbicide toxicity to the green unicellular alga Chlamydomonas eugametos and three major weeds (Xanthium pennsylvanicum, Abutilon theophrasti, and Ipomoea sp.). Acifluorfen-methyl and MC 15608 toxicity in Chlamydomonas decreased in an atmosphere of nitrogen, and in the presence of the free radical scavengers α-tocopherol and ethanol. Therefore, the mechanism of toxic action of these three different diphenyl ether herbicides is similar and appears to involve some type of free radical reaction. As confirmed by cyclic voltammetry studies, MC 15608 and MC 10878, unlike AFM, cannot readily accept electrons to become free radicals. Therefore, initiation of free radical reactions in polyunsaturated fatty acids of membranes does not necessarily involve direct reduction and reoxidation of the diphenyl ether molecule.     

磺酰脲类除草剂与杂草对其抗性的研究进展

1磺酰脲类除草剂的概况1.1磺酰脲类除草剂的发展20世纪70年代末,美国杜邦公司Levitt等首次开发和报道了磺酰脲类除草剂绿磺隆的除草活性[1]。80年代初,这一除草剂开始进行大规模商品化生产,此后,又不断研制和开发了许多磺酰脲类除草剂新品种。此类除草剂问世以后,以其活性高、选择性强、杀草谱广及对动物安全等特性在世界各地得到广泛应用。目前有关磺酰脲类除草剂的专利有400多项,已商品化的有30多种。这类除草剂有很高的除草效率,用量一般为2~100 g/hm2,比传统除草剂的除草效率高100~1 000倍[2]。磺酰脲类除草剂对动物低毒,在非靶标生物…     

Studies into the action of the diphenyl ether herbicides acifluorfen and oxyfluorfen. Part II: The interaction with photosynthetic electron transport reactions

The effects of acifluorfen and oxyfluorfen on photosynthetic electron transport reactions of pea chloroplasts were compared with those induced by paraquat and monuron. Monuron inhibited electron flow between photosystems I and II, and paraquat acted as an electron acceptor for photosystem I, promoting superoxide formation by illuminated chloroplasts. Neither acifluorfen nor oxyfluorfen at concentrations up to 50 μM affected non-cyclic electron flow or promoted superoxide formation. Both herbicides were shown to repress ferredoxin-dependent NADP⁺ reduction by illuminated chloroplasts. Further experiments showed that, in the presence of ferredoxin-NADP⁺ reductase and chloroplast membranes maintained in the dark, p-nitro diphenyl ether (DPE) herbicides promoted the rate of ferredoxin-dependent oxidation of NADPH, implying that these herbicides can accept electrons from reduced ferredoxin. The interaction between acifluorfen, ferredoxin and chloroplast membranes was examined further by following the effect of this herbicide on the peroxidation of illuminated thylakoids. Lipid peroxidation was promoted by acifluorfen, although this effect was abolished if thylakoids were washed prior to use. The effect of washing could be reversed by adding exogenous ferredoxin. These data demonstrate that interaction of DPE herbicides with photosynthetic electron transport in the vicinity of ferredoxin is necessary for light-dependent herbicide activation.     

Studies into the action of the diphenyl ether herbicides acifluorfen and oxyfluorfen. Part I: Activation by light and oxygen in leaf tissue

The effect of acifluorfen and oxyfluorfen on chlorophyll bleaching, lipid peroxidation and photosynthesis in pea leaf discs was studied. Both her- bicides induced light-dependent bleaching and lipid peroxidation, the level of damage being greater at higher light intensities. Photosynthetic carbon dioxide fixation was only partially inhibited in treated leaf discs incubated in darkness, thus indicating that these herbicides did not inhibit photo- synthesis as a primary mode of action. Leaf discs maintained in darkness showed no visible signs of injury, and light-dependent herbicide-induced damage was reduced by incubating discs under nitrogen, orpre-incubating them with the electron-transport inhibitor monuron. It is suggested that acifluorfen and oxyfluorfen are activated by a light-dependent process, which requires photosynthetic electron transport.     

A novel genomic approach to herbicide and herbicide mode of action discovery

A herbicide with a new mode of action has not been commercialized for more than 30 years. A recent paper describes a novel genomic approach to herbicide and herbicide mode of action discovery. Analysis of a microbial gene cluster revealed that it encodes genes for both the biosynthetic pathway for production of the sesquiterpene aspterric acid and an aspterric acid‐resistant form of dihydroxy acid dehydratase (DHAD), its target enzyme. Aspterric acid is weak compared with commercial synthetic herbicides, and whether DHAD is a good herbicide target is unclear from this study. Nevertheless, this genomic approach provides a novel strategy for the discovery of herbicides with new modes action. © 2018 Society of Chemical Industry     

Study of the enhancement of herbicide activity and rainfastness by an organosilicone adjuvant utilizing radiolabelled herbicide and adjuvant

‘Sylgard® 309’ organosilicone surfactant is a very effective adjuvant for broadleaf weed control with a number of herbicides. It is also effective in providing rainfastness lo these post-emergence herbicide applications. To elucidate the basis for herbicide activity enhancement and rainfastness, the absorption of [¹⁴C]acifluorfen, [¹⁴C]bentazone and [¹⁴C]‘Sylgard 309’ were studied. Non-ionic surfactants and crop oil concentrates were used as adjuvants with [¹⁴C]acifluorfen and [¹⁴C]bentazone, respectively, for purposes of comparison. Maximum absorption of [¹⁴C]acifluorfen and [¹⁴C]bentazone was obtained within 15 min after herbicide application with the organosilicone, versus ≥ 24 h with the convenlional adjuvants. [¹⁴C]-Organosilicone absorption closely paralleled that of the [¹⁴C]-herbicides. The organosilicone appears to exert its action by increasing greatly herbicide absorption. The enhancement effect did not appear to be a function of reduced surface tension. Rainfastness appeared to be a result of greatly accelerated herbicide penetration through the leaf cuticle in the presence of the organosilicone.     

除草剂的药害及其预防

不是人们有意识栽培的植物即是杂草,它们与作物没有本质的区别,人们在化学除草的同时也会对作物产生或多或少的影响,当这种影响超出作物的忍受范围时,就构成了药害。随着化学除草的普及,药害问题也越来越突出。河南省近几年就发生化除药害大事故上百起,受害作物面积达66.7万hm~2。1988年的盐城发生小麦百草敌药害,1996年江苏省水稻秧苗发生扫茀特药害等大事故。除草剂     

安全剂R-28725保护玉米免受氯磺隆药害的作用

采用生物测定法研究了安全剂R-28725保护玉米免受除草剂氯磺隆药害的作用.在氯磺隆毒土浓度为2 μg/kg时,使用5mg/kgR-28725浸种处理,玉米根部受到氯磺隆抑制的谷胱甘肽(GSH)含量由空白对照的57.3％恢复至83.4％;玉米叶片中乙酰乳酸合成酶(ALS)活性增加了17.2％;玉米根部的谷胱甘肽-S-转移酶(GST)活性增加了191.8％;GST酶促反应动力学参数Vmax增大102.5％,Km减小40.0％.结果显示:R-28725能够提高氯磺隆处理后玉米中GSH的含量,增加GST和ALS活性,增强了玉米根部GST酶对底物的亲和力,缓解氯磺隆对玉米产生的药害.     

Competition between a thiocarbamate herbicide and herbicide protectants at the level of uptake into maize cells in culture

The rapid interactions between the herbicide S-ethyl dipropyl thiocarbamate (EPTC) and the structurally similar herbicide protectant N,N-diallyl 2,2-dichloroacetamide (DDCA) at the level of herbicide uptake were examined in maize cell cultures. When the two compounds were given simultaneously, DDCA inhibited uptake of [¹⁴C]EPTC into maize cells measured for 30 min. A Lineweaver-Burk plot indicated this inhibition to be competitive. N,N-Diallyl 2-chloroacetamide (CDAA), a compound similar in structure to DDCA, inhibited uptake to a lesser extent. Other protectants having no similarity in structure to either DDCA or EPTC had no inhibitory effect on the uptake of EPTC. The data suggest that competition between DDCA and EPTC for a site of uptake may be related to their similarity in chemical structure. Experiments with metabolic inhibitors suggested that uptake of EPTC is not via an active transport mechanism. We suggest that competition for uptake between EPTC and DDCA may represent the first step in a complex series of interactions between the herbicide and its protectant that contributes to the protection of maize from herbicide injury.     

The photochemical decomposition of the herbicide isoproturon

The photochemical degradation of the herbicide isoproturon in aqueous and non-aqueous solutions and in soils has been investigated. Four new photometabolites were formed in non-aqueous solution and three in soil. These were characterised by spectroscopic methods and identified by comparison with authentic synthetic samples such as 3-(4-isopropylphenyl)-1-methylurea; 3-(4-isopropylphenyl)urea; 4,4′-diisopropylazobenzene and 4,4′-diisopropylazoxybenzene. The pathway of formation of these photo products is depicted.     

Degradation of the herbicide flamprop-methyl in soil

The degradation of the wild oat herbicide flamprop-methyl [methyl DL -N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate] in four soils has been studied under laboratory conditions using ¹⁴C-1abelled samples. The flamprop-methyl underwent degradation more rapidly than its analogue flamprop-isopropyl. However, similar degradation products were formed, namely the corresponding carboxylic acid and 3-chloro-4-fluoroaniline. The latter compound occurred mainly as ‘bound’ forms although evidence was obtained of limited ring-opening to give [¹⁴C]carbon dioxide. The time for depletion of 50% of the applied herbicide was approximately 1-2 weeks in sandy loam, clay and medium loam soils and 2-3 weeks in a peat soil.     

除草剂药害原因及预防

化学除草因省工省时、除草效率高而深受广大农民的青睐,化学除草面积逐年扩大.随着化学除草剂在各类农作物田广泛推广应用,有效地控制了农田杂草的发生与危害,实现了农作物的增产.     

三嗪类除草剂莠去津的研究进展

三嗪除草剂莠去津是在世界范围内广泛应用的一种除草剂,其对人类健康、农业生产及生态环境的影响具有全球性,已经引起广泛关注。本文介绍了莠去津的性质、危害、迁移分布、分析检测及相关的法规。     

除草剂中的安全剂研究进展

综述除草剂中安全剂的应用历史、国内外研究现状、分类、目前商业化种类及应用情况,较为系统地介绍了其作用机制,并展望了安全剂的发展前景。     

Hydrolysis of the triazine herbicide,cyanazine

The hydrolysis of cyanazine

1 Cyanazine is the proposed common name for the herbicide sold under the Shell registered trade name BLADEX.

(2-chloro-4-cyanoisopropylamino-6-ethylamino-1,3,5-triazine) has been studied using ¹⁴C-ring labelled compound over a temperature range of 25° to 75 °C and over a range of pH values from 1.5 to 12. The activation energies and the activation entropy changes during hydrolysis showed there was a different mechanism under acid and alkaline conditions. The only product identified after hydrolysis in acid solutions was 2-hydroxy-4-carboxyisopropylamino-6-ethylamino-1,3,5-triazine. In alkaline solution the same hydroxy-acid was the end-product, but 2-chloro-4-amidoisopropylamino-6-ethylamino-1,3,5-triazine was isolated as an intermediate. The variation of the specific rate constants with temperature for hydrolytic catalysis by H⁺, OH^? was determined, thus enabling the hydrolytic half-life of cyanazine to be calculated at any pH and temperature.     

Degradation of the herbicide benzoylprop-ethyl in soil

The degradation of [¹⁴C] benzoyl prop ethyl (SUFFIX,^a ethyl N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate) in four soils has been studied under laboratory conditions. The major degradation product of benzoylprop ethyl at up to 4 months after treatment was its corresponding carboxylic acid (II). On further storage this compound became firmly bound to soil before it underwent a slow debenzoylation process which led to the formation of a number of products including N-3,4-dichlorophenylalanine (IV), benzoic acid, 3,4-dichloroaniline (DCA), which was mainly present complexed with humic acids, and other polar products. Although these polar products were not identified, they were probably degradation products of DCA, since they were also formed when DCA was added to soil. No 3,3′,4,4′-tetrachloroazobenzene (TCAB) was detected in any of the soils at limits of detectability ranging from 0.01-0.001 parts/million. Since N-3,4-dichlorophenylalanine (IV) and 3,4-dichloroaniline were transient degradation products of benzoylprop ethyl, the metabolism in soil of radiolabelled samples of these compounds was also studied. In these laboratory experiments the persistence of the herbicide increased as the organic matter content of the soil increased and the time for depletion of half of the applied benzoylprop ethyl varied from 1 week in sandy loam and clay loam soils to 12 weeks in a peat soil.