Herbicide activity involving light

The effect of light on the activity of herbicides within the cell is reviewed. The herbicides are grouped according to the way their phytotoxicity is influenced by light. The largest group, which includes the ureas, triazines and uracils, interfere with photosynthesis by blocking the Hill reaction. Lack of carbohydrates and other manifestations of toxicity appear in the light and these are discussed. The bipyridylium quaternary salts, diquat and paraquat, are not phytotoxic until a free radical is formed utilising light energy via photosynthesis. The free radical is re-oxidised by molecular oxygen, and a series of reactions are started leading to the formation of peroxide radicals which subsequently disrupts the cell. The phytotoxicity of 2,4-dinitrpphenol and related compounds is reduced by light. This type of compound combined with a herbicide which inhibits the Hill reaction and thus photosynthetic phosphorylation may act synergistically and mixtures of this type are discussed.     

Target sites for herbicides: entering the 21st century

At present the use-rate of modern herbicides is in the range of 100-300 g AI ha-1, with a tendency to decline. The low use-rate (ca 10 g AI ha-1) of the original sulfonylurea and cyclic imide herbicides prompted agrochemical scientists to look for even more active compounds which led to the successive discoveries of many new herbicidal acetolactate synthase inhibitors and no less than 18 cyclic imides in the class of protoporphyrinogen-IX oxidase inhibitors in the 1990s. In this paper, mechanisms of action related to function and biosynthesis of chlorophylls, carotenoids, plastoquinone, amino acids, fatty acids and photosynthetic electron transport and other metabolic processes are discussed as plant-specific herbicidal target domains.     

Influence of herbicides on photosynthetic activity and transpiration rate of intact plants

The effect of various herbicides on photosynthesis, respiration and transpiration of intact plants has been studied in a routine assembly. Simultaneous measurements were made under different experimental conditions in four small plant chambers, in which the shoots of various plant species can be accommodated. The herbicide is applied during measurement, so that the effect can be related to the photosynthetic activity of the same plants before treatment. The selectivity of various herbicides was studied by determining the capacity of a plant species to inactivate a herbicide absorbed by the roots. These and other differential effects of various herbicides on photosynthetic activity of different plant species coincide with the selective properties in the field. Such differences are also observed after leaf sprayings. The duration of the experiments is kept short. Bean plants were studied under various experimental conditions of air humidity, light intensity and temperature resulting in different transpiration rates. The decrease in photosynthetic activity owing to the presence of a herbicide in the nutrient solution at a standard concentration was more rapid at the higher transpiration rates. The total transpiration during treatment up to 50% inhibition of photosynthesis was constant under the various experimental conditions. Specific inhibitors of the photosynthetic process had a more pronounced effect on the photosynthetic activity than on transpiration rate. Some other herbicides affect transpiration as well as photosynthesis.     

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.     

Formation of nitrite in plants treated with herbicides that inhibit photosynthesis

Avena sativa and Sinapis alba plants were sprayed with selected herbicides and time was allowed for the herbicides to penetrate into the plants. The plants were then illuminated in a nitrogen atmosphere for 60 min. Nitrite (up to 600 nmol/g fresh weight) was found in plants treated with herbicides that inhibit photosynthesis; these plants died a few hours later. Nitrite (up to 408 nmol/g fresh weight) was found in plants treated with herbicides that uncouple oxidative phosphorylation, but here the highest values were obtained after incubation in air. No nitrite was found in control plants incubated in nitrogen or in plants treated with photosynthesis-inhibiting herbicides and incubated in air. Experiments with plants either grown on different nitrogen sources or adapted to different light intensities rule out the possibility that the damage observed in the plants could be caused by nitrite. Possible reasons for the herbicidally induced damage are discussed.     

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.     

除草剂中光合作用抑制剂的研究

文章阐述了除草剂中的几类光合作用抑制剂,其抑制途径与作用机理,以及除草剂中光合作用抑制剂的研究进展。     

Synthesis and thylakoid membrane binding of the radioactively labeled herbicide dinoseb

2,4-Dinitro-6-isobutylphenol (i-dinoseb), an isomer of the phenolic herbicide dinoseb and equally active as an inhibitor of photosynthetic electron transport and photophosphorylation, has been synthesized, ³H-labeled with a specific activity of 490 mCi/mmol. Its binding to broken chloroplasts is strongly pH dependent and biphasic representing a high- and a low-affinity binding site. For specific binding of i-dinoseb a binding constant K_b = 6.9 × 10^?8M has been determined. The number of binding sites corresponds to one molecule i-dinoseb per 830 molecules of chlorophyll, i.e., one molecule per two electron transport chains. i-Dinoseb can be displaced from the thylakoid membrane by DCMU-type inhibitors, and inhibitory uncouplers, but not by DBMIB-type inhibitors and uncouplers of oxidative phosphorylation. An extensive analysis of displacement by DCMU-type and phenolic herbicides indicates that DCMU-type herbicides interfere noncompetetively but phenolic herbicides interfere competetively with the specific binding of i-Dinoseb. It is concluded, therefore, that the binding sites of both types of herbicides are not identical although they are located on the same protein. The specific binding constant of i-dinoseb does not change in trypsin-treated chloroplasts whereas the number of binding sites is slightly reduced.     

Chlorophyll fluorescence as a marker for herbicide mechanisms of action

Photosynthesis is the single most important source of O₂ and organic chemical energy necessary to support all non-autotrophic life forms. Plants compartmentalize this elaborate biochemical process within chloroplasts in order to safely harness the power of solar energy and convert it into usable chemical units. Stresses (biotic or abiotic) that challenge the integrity of the plant cell are likely to affect photosynthesis and alter chlorophyll fluorescence. A simple three-step assay was developed to test selected herbicides representative of the known herbicide mechanisms of action and a number of natural phytotoxins to determine their effect on photosynthesis as measured by chlorophyll fluorescence. The most active compounds were those interacting directly with photosynthesis (inhibitors of photosystem I and II), those inhibiting carotenoid synthesis, and those with mechanisms of action generating reactive oxygen species and lipid peroxidation (uncouplers and inhibitors of protoporphyrinogen oxidase). Other active compounds targeted lipids (very-long-chain fatty acid synthase and removal of cuticular waxes). Therefore, induced chlorophyll fluorescence is a good biomarker to help identify certain herbicide modes of action and their dependence on light for bioactivity.     

The determination of trace levels of ethylenethiourea

All currently utilized herbicides have been identified by random screening and related compounds developed by subsequent imitative chemistry. Little success has as yet been achieved by rational design. Ideas for herbicide design are discussed in relationship to enzyme inhibition, enzyme regulation and the accumulation of toxic metabolites. A number of herbicides in current use function either by promoting the formation of toxic radicals or by inhibiting protective systems. There is scope for the development of protective enzyme inhibitors, as well as the modulation of other scavenging systems. Natural or synthetic photosensitizers as well as a number of allelopathic chemicals could be used as herbicides. Herbicide selectivity could be investigated by the selective inhibition of C⁴ photosynthesis enzymes, by a detailed examination of enzyme diversity, or by the modulation of mono-oxygenase enzymes or glutathione conjugation.     

Quantitative structure-activity relationships of the inhibition of photosynthetic electron flow by substituted diphenyl ethers

The effect of 41 substituted diphenyl ethers (derivatives of nitrofen and chloroxuron) on photosynthesis in isolated spinach chloroplasts has been studied. All the chemicals were found to be inhibitors of non-cyclic electron transport; the pI₅₀ values varied from 3.17 to 7.16 (I₅₀ is the molar concentration causing 50% inhibition; pI₅₀= -log I₅₀). Based on their structures, the compounds were divided into four groups; for most groups, a correlation between the inhibition of photosynthesis and physicochemical parameters was found. Lipophilicity proved to be the most important parameter; electronic effects did not play a role. Introduction of substituents into the nitrophenyl ring of nitrofen lowered activity considerably. Nitrofen and and chloroxuron analogues seemed to inhibit at different sites in the electron transport chain. A relationship between inhibition of photosynthesis and herbicidal activity was not clear.     

Changes in free amino acid pools can predict the mode of action of herbicides

Studies were conducted to determine the short-term changes in free amino acid levels in the meristematic zone of maize after treatment with various herbicides with different modes of action. These herbicides included inhibitors of various amino acid biosynthetic pathways, photosynthesis, and fatty acids biosynthesis. Inhibitors of various amino acid biosynthetic pathways caused specific reduction in the pools of amino acids being produced by the particular pathway. Inhibitors of other metabolic pathways also caused significant changes in pools of various amino acids. Very similar changes in the pools of amino acids were seen in plants treated with different chemical classes of inhibitors affecting a certain metabolic pathway. However, the changes were quite different between inhibitors of different metabolic processes. The data generated from these studies could be used as a diagnostic tool to determine the mode of action of novel herbicides.     

对羟基苯基丙酮酸双氧化酶抑制剂筛选方法研究进展

对羟基苯基丙酮酸双氧化酶(HPPD)是植物体正常生长所必需的质体醌和生育酚生物合成路径中的关键酶,已成为当前最重要的除草剂作用靶标之一。发展快速、可靠的HPPD抑制剂筛选方法对研究小分子化合物与HPPD之间的相互作用,以及开展基于靶酶结构的新型HPPD抑制剂设计均具有重要意义。结合HPPD的结构和功能,文章从生物分析的角度分别就高效液相色谱、同位素标记、偶联法、电化学及简易筛选模型等方法在HPPD抑制剂筛选中的运用进行了总结,并对发展HPPD抑制剂的高通量筛选方法进行了展望。     

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.     

Sites of action of photosynthetic inhibitor herbicides; Experiments with trypsinated chloroplasts

The effect of four photosynthetic inhibitor herbicides, bromacil, ioxynil, metribuzin and monuron, on chloroplast electron transport was investigated. All four compounds completely inhibited electron flow with tripotassium hexacyanoferrate as oxidant, but the inhibition caused by bromacil, metribuzin and monuron was almost totally reversed by trypsin treatment. With ioxynil, only a partial degree of reversability was shown. With a molybdosilicate as oxidant, electron transport was not completely inhibited by any of the herbicides. Whereas the partial inhibition was reversed by tryptic digestion in the presence of bromacil, metribuzin and monuron, there was virtually no reversal in the presence of ioxynil. The results suggest a common site of action for all four herbicides and an additional site for ioxynil nearer to photosystem II.     

HPPD抑制剂的机理与应用进展

HPPD是在植物光合作用过程中发现的一类新型除草剂靶标酶,可以催化对羟苯基丙酮酸氧化脱羧转变为尿黑酸。HPPD抑制剂的抑制作用会导致植物分生组织产生白化症状,最终死亡。本文对HPPD的作用机理以及HPPD抑制剂主要品种的应用作了综述。     

Photosynthesis and growth responses of grapevine to acetochlor and fluoroglycofen

Acetochlor and fluoroglycofen are herbicides used in vineyards to eradicate weeds. This present study characterized the effects of these chemicals on photosynthetic characteristics and the antioxidant enzyme system in non-target grape leaves. The results showed that acetochlor and fluoroglycofen reduced net photosynthetic rate in a dose-dependent manner, but also reduced or increased pigment contents, respectively. According to chlorophyll fluorescence measurements, acetochlor and fluoroglycofen decreased the photochemical efficiency of photosystem II in the light and increased non-photochemical quenching. These herbicides enhanced malondialdehyde contents and accelerated the superoxide anion production rate in dose-dependent manners, which might be associated with lower antioxidant enzyme activities, especially at higher concentrations of the herbicides. Acetochlor and fluoroglycofen inhibited grapevine growth in the growth season one-year after herbicide treatment, and stem height was inhibited by up to 55.4% and 88.0%, respectively. Taken together, these results suggest that both herbicides are detrimental for grape photosynthesis and this might be associated with increased oxidative stress in the first year, while growth inhibition in the second year might be due to after effects of herbicide treatment.     

Phytotoxic sites of action for molecular design of modern herbicides (Part 1): The photosynthetic electron transport system

A bird's eye review was tried to select the bio‐rational targets from known and novel plant‐specific ones for the molecular design of modern herbicides, which exhibit efficient phytotoxicity at a low‐use rate and preserve a good environment in the 21st century. In phytotoxic sites in the photosynthetic electron transport (PET) system discussed in the present article (Part 1), the generally called bleaching herbicides interfering with the biosynthesis of photosynthetic pigments, chlorophylls and carotenoids, and the biosynthesis of plastoquinone, were considered to be good models for the molecular design of modern herbicides. The PET itself was still considered as an interesting target site for new herbicides, although they need to exert their action in all green leaves of weeds to achieve herbicidal efficacy. Because these herbicides never form a tight binding with D1‐protein, their use‐rate cannot be expected to be as low as the herbicides inhibiting chlorophyll or branched amino‐acid biosynthesis. Other herbicidal targets found in chloroplasts, namely ATP and NADPH formations, have already been omitted from the worldwide biorational molecular design program of herbicides targeting the PET system.     

Jack bean urease inhibition by substituted ureas

The increased use of urea fertilizer and substituted ureas herbicides, the implication of soil urease in the effectiveness of urea applied as fertilizer, makes necessary to investigate their relationship.All herbicides investigated, fenuron, monuron, diuron, linuron, siduron and neburon are urease inhibitors. The inhibition constant value depends on molecular groups on the urea skeleton. There is a linear relationship between the Hammett sigma values and log Ki for fenuron, monuron and diuron.The presence of a large hydrophobic group and of one or two chlorine—an electron withdrawing group—on the phenyl ring of the herbicides molecule influences the Ki value.The hypothesis is proposed that the enzyme molecule reacts with inhibitors by means of the oxygen atom of the carboxyl group in the substituted ureas.     

The effect of substituted urea herbicides on the growth of excised tomato roots

The action of 23 herbictdal substituted ureas on the growth of excised tomato roots was studied in order to détérmine whether there is a link between the effects of these herbicides on oxidative phosphorylation and on the growth of non-photosynthetic tissues. Fourteen of these herbicides were inhibitory; chlortoluron and TBU were stimulatory but only in the light. Substituted ureas known to affect plant mitochondria inhibited root growth but to a lesser extent than some which had no action on mitochondria. No clear relationship was found between actions on mitochondria and on root growth. It is suggested that targets other than photosynthesis and oxidative phosphorylation exist for some substituted ureas.