The possible role of quinate in the mode of action of glyphosate and acetolactate synthase inhibitors

BACKGROUND: The herbicide glyphosate inhibits the biosynthesis of aromatic amino acids by blocking the shikimate pathway. Imazethapyr and chlorsulfuron are two herbicides that act by inhibiting branched‐chain amino acid biosynthesis. These herbicides stimulate secondary metabolism derived from the aromatic amino acids. The aim of this study was to test if they cause any cross‐effect in the amino acid content and if they have similar effects on the shikimate pathway. RESULTS: The herbicides inhibiting two different amino acid biosynthesis pathways showed a common pattern in general content of free amino acids. There was a general increase in total free amino acid content, with a transient decrease in the proportion of amino acids whose pathways were specifically inhibited. Afterwards, an increase in these inhibited amino acids was detected; this was probably related to proteolysis. All herbicides caused quinate accumulation. Exogenous application of quinate arrested growth, decreased net photosynthesis and stomatal conductance and was ultimately lethal, similarly to glyphosate and imazethapyr. CONCLUSIONS: Quinate accumulation was a common effect of the two different classes of herbicide. Moreover, exogenous quinate application had phytotoxic effects, showing that this plant metabolite can trigger the toxic effects of the herbicides. This ability to mimic the herbicide effects suggests a possible link between the mode of action of these herbicides and the potential role of quinate as a natural herbicide. Copyright © 2009 Society of Chemical Industry     

STUDIES ON HERBICIDE CONTENTS IN ROOTS OF SKELETON WEED (CHONDRILLA JUNCEA L.) FOLLOWING LEAF APPLICATIONS

Summary. The herbicides studied were 2,4-D, 2,4-DB, dicamba and orthoarsenic acid. Herbicide content in the roots was taken as an overall measure of penetration into and absorption by the leaves, and of translocation to the roots.
A significantly greater 2,4-D content resulted from foliar application at pH 3–5 than at higher values, though at pH 8–5 the inclusion of triethanolamine significantly increased the 2,4-D content. No evidence was obtained that a greater 2,4-D content should result from foliage applications of 2,4-DB than from 2,4-D. Dicamba gave a greater herbicide content than 2,4-D when applied at high concentration at 20° C but not at 25° C, probably because of less injury at the lower temperature.
Concentrations of Tween 20 up to 2% had no deleterious effect on the 2,4-D content; on the other hand 2,4-D content was lowered by 0–25% or more of cetyltrimethyl-ammonium bromide. Poor wetting is not the cause of the variable herbicide contents sometimes obtained.
Orthoarsenic acid, which has given better control of the weed than 2,4-D, was very poorly translocated; its effectiveness is due to its high intrinsic toxicity.
Etudes sur la teneur en herbicide des racines de Chondrilla juncea L. á la suite d'applications sur les feuilles     

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.     

A review of the effects of humidity, humectants, and surfactant composition on the absorption and efficacy of highly water-soluble herbicides

It is well known that environmental conditions have an important influence on herbicide efficacy. In particular, the effect of humidity on herbicide uptake has been attributed to changes in cuticle hydration and droplet drying. As early as the 1950s, it was hypothesized that humectants such as glycerol would enhance herbicide uptake by not letting droplets dry, thus maintaining the herbicide in solution, and hence making it available for uptake. Shortly thereafter, evidence was found to support this hypothesis and humectants were used successfully in warm, dry areas to increase herbicide efficacy. However, by the mid-1980s, there was little use of humectants as research on humectants gave way to investigations on the effect of ethylene oxide (EO) content on surfactant performance to improve herbicide uptake and efficacy. While ethoxylated surfactants effectively increase the uptake of both lipophilic and hydrophilic herbicides, the suggestion that long EO chains have humectant properties is misleading, since the studies that led to this suggestion were performed at high humidity, which would prevent rapid droplet drying. Furthermore, current evidence suggests that highly water-soluble, ionic herbicides may be more sensitive to low humidity and rapid drop drying than lipophilic herbicides. Therefore, an overview is presented on the interaction of water-soluble herbicides with surfactants, the cuticle, and humidity, with particular emphasis on the impact of low humidity and humectants on herbicide uptake. It was found that when one focuses on research performed at low humidity the importance of humectants emerges, which is not in keeping with what is now commonly accepted.     

An investigation of herbicide interaction with the H+-ATPase activity of plant plasma membranes

This study has investigated the activity of several herbicide classes at the plant plasma membrane. Two-phase partitioning was used to prepare highly purified plasma membrane vesicles from the monocotyledon weed black-grass (Alopecurus myosuroides Huds.) and the dicotyledon crop sugar beet (Beta vulgaris L. cv. Celt). The purity of the plasma membrane H⁺-ATPase activity was characterised with respect to inhibitors, pH and substrate specificity. In both species, contamination of the plasma membrane by tonoplast fragments was largely eliminated and chlorophyll was absent. In addition, the plasma membrane H⁺-ATPase from black-grass and sugar beet exhibited high vanadate sensitivity and a sharp pH profile around 6·5. Subsequently, H⁺-ATPase activity was assayed in the presence (100 μM ) and absence of four graminicide classes and auxin-type herbicides. Graminicides, including the aryloxyphenoxypropionate diclofop-methyl and the thiocarbamate triallate, inhibited H⁺-ATPase activity by 50–80% in both species. However, other graminicides, including the cyclohexanediones and the chloroacetamide alachlor, had no affect. Similarly, auxin-type herbicides such as 2,4-D and MCPA did not inhibit H⁺-ATPase activity. Results are discussed in relation to the proposed mode of action of these herbicides. © 1998 SCI     

The influence of additives on the penetration of foliar applied growth regulator herbicides

The possibilities are demonstrated of increasing the activity of foliar applied growth regulator herbicides by mixing them with chemicals which injure the cuticle or epidermis. S, S, S-Tributyl phosphorotrithioate (“DEF”) increases the effects of picloram, 2,4,5-T and mecoprop salts on four woody species, privet (Ligustrum ovalifolium Hassk.), poplar (× Populus gelrica Ait.), bluegum (Eucalyptus globulus Labill.) and guava (Psidium guajava L.). Mixtures with esters of the herbicides are not synergistic and often antagonistic. DEF, tributyl phosphorotrithioite, a number of alkyl and aryl phosphates and phosphites and potassium ethyl xanthate enhance the phytotoxicity of picloram solution on dwarf bean (Phaseolus vulgaris L.). Mixtures of picloram with tributyl phosphorotrithioite, tributyl phosphate, mixed acid butyl phosphates, trimethyl phosphate and mixed isomers of tritolyl phosphate are synergistic when applied to guava foliage. Tributyl phosphate and mixed acid butyl phosphates interact similarly with picloram on privet and tributyl phosphate increases the effects of foliar applied mecoprop salt on guava. The mode of action of the additives is not fully understood but there is evidence that DEF facilitates the entry of water soluble growth regulator herbicides into leaves and has little effect on the rate at which the herbicides move through the plant. Tributyl phosphate and mixed acid butyl phosphates are suggested for practical use in herbicide formulations to control woody plants, as they are relatively cheap and non-toxic.     

Structural aspects of the knockdown of pyrethroid

The polarities of pyrethroids and their performance as knockdown and killing agents against houseflies are discussed. The optimum polarity for knockdown is here shown to be greater than that needed for kill, probably because knockdown depends on relatively rapid penetration through the cuticle into the haemolymph and thence to the site of action.     

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.     

Recent developments in our understanding of the plant cuticle as a barrier to the foliar uptake of pesticides†

The plant cuticle is a highly complex membrane which forms the outer surface of the aerial portion of plants. The nature of the plant cuticle is reviewed with particular regard to its action as a potential barrier to the penetration of pesticide molecules; the role of the cuticular waxes is highlighted. The physicochemical properties of the cuticle influence the behaviour of spray droplets and, in turn, may affect the rate and efficiency of cuticle penetration. The permeation of active ingredients is influenced by their solubility characteristics as indicated by octanol/water (log K_ow) and cuticle/water (K_cw) partition coefficients. Penetration of hydrophilic compounds (low log K_ow) may be enhanced by hydration of the cuticle, while transcuticular transport of non-polar solutes (high log K_ow) is increased by factors which reduce wax viscosity. The use of in-vitro models involving isolated cuticle membranes, isolated cuticle waxes, or isolated leaves has helped to focus on the activities of the cuticle in the absence of other physiological factors. Using these systems, the role of the waxes as a transport-limiting barrier has been identified and the factors influencing sorption, permeance and desorption examined. The action of surfactants, in vitro and in vivo, has been briefly addressed in regard to their role in facilitating cuticle penetration; other steps involving surfactant/solute/cuticle are complex, and synergy appears to depend on a number of factors including test species, concentration of active ingredient, surfactant type and concentration. Adjuvants may greatly influence the surface properties of the droplet, predispose the cuticle to solute transport, and enhance pesticide activity. The nature of these complex inter-relationships is discussed. © 1999 Society of Chemical Industry     

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     

Plant cell membrane as a marker for light-dependent and light-independent herbicide mechanisms of action

Plant cells possess a number of membrane bound organelles that play important roles in compartmentalizing a large number of biochemical pathways and physiological functions that have potentially harmful intermediates or by-products. The plasma membrane is particularly important as it holds the entire cellular structure whole and is at the interface between the cell and its environment. Consequently, breaches in the integrity of the lipid bilayer, often via reactive oxygen species (ROS)-induced stress membrane peroxidation, result in uncontrolled electrolyte leakage and in cell death. A simple 3-step bioassay was developed to identify compounds that cause electrolyte leakage and to differentiate light-dependent mechanisms of action from those that work in darkness. Herbicides representative of all known modes of action (as well as several natural phytotoxins) were selected to survey their effects on membrane integrity of cucumber cotyledon discs. The most active compounds were those that are known to generate ROS such as the electron diverters and uncouplers (paraquat and dinoterb) and those that either were photodynamic (cercosporin) or caused the accumulation of photodynamic products (acifluorfen-methyl and sulfentrazone). Other active compounds targeted lipids (diclofop-methyl, triclosan and pelargonic acid) or formed pores in the plasma membrane (syringomycin). Herbicides that inhibit amino acid, protein, nucleotide, cell wall or microtubule synthesis did not have any effect. Therefore, it was concluded that the plant plasma membrane is a good biomarker to help identify certain herbicide modes of action and their dependence on light for bioactivity.     

Classification of herbicides according to chemical family for weed resistance management strategies – an update

There are inaccuracies in the chemical families of the WSSA and HRAC herbicide classification systems which could limit their practical use in herbicide‐based weed management strategies. In essence, these inaccuracies could be divided into four parts: (i) the nomenclature of many of the chemical families is not correct, (ii) distinct active ingredients are grouped in same chemical families, (iii) many chemical families have been repeated in at least two modes of action/herbicide groups, and (iv) many active ingredients have not been assigned to chemical family, herbicide group or mode of action. The aim of this study was to revise the current classifications and to propose corrections for the current ones. Detailed investigations on chemical structure of the active ingredients of the registered herbicides showed that some moieties have the same mechanisms of action. According to this study, these moieties have been assigned to the names of chemical families and active ingredients are then classified within the chemical families accordingly. This study has 119 chemical families, compared with 145 in the WSSA system and 58 in the HRAC system. A major priority of this study is the number of active ingredients covered; we included 410 active ingredients with known mechanisms of action and herbicide groups, more than 100 active ingredients more than the current classification systems. Overall, this study provides better opportunities for the management of resistance to herbicides through the application of improved pure and applied knowledge.     

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.     

Challenges for herbicide resistance evolution and management: 50 years after Harper

Evolved resistance to herbicides is a classic example of ‘evolution in action’. This paper calls for a greater integration of ‘evolutionary‐thinking’ into herbicide resistance research. This integration, it is argued, should lead weed scientists to become less focused on simply describing resistance and more driven towards a deeper understanding of the evolutionary forces that underpin resistance evolution. I have attempted in this short paper to initiate a debate into how this might be done. In the first instance, I have highlighted the widespread misunderstanding and mis‐measurement by weed scientists of fitness and fitness costs. I have also speculated on the potential for herbicide rotations to exacerbate resistance problems by selecting for generalist (metabolic) resistance. Finally, I have discussed in greater detail the contribution of herbicide rates to resistance evolution and have reported work conducted in Australia which has shown the potential for low herbicide doses to rapidly select for very high levels of resistance in Lolium rigidum. The controversial hypotheses and suggestions put forward need to be tested by field experimentation. They may prove to be unfounded or incorrect, but if they cause us to question and expand the current resistance paradigm they will have been useful.     

Phytotoxic activity of middle-chain fatty acids II: peroxidation and membrane effects

Pelargonic acid (PA), an aliphatic 9-carbon monocarboxylic acid, is a phytotoxic burn-down compound. In the light peroxidizing activity can be measured as ethane and propane formation with cress or tobacco seedlings. This effect is strong at low pH (4–5), and saturated acids with 9–10 carbon atoms represent the optimum chain length. Methyl or ethyl esters are inactive, and safeners have no influence. In contrast to the peroxidative herbicides like acifluorfen methyl neither photosynthesis nor protoporphyrin IX is involved, although peroxidation requires light. Chlorophyll is necessary since etiolated seedlings show little peroxidation. Singlet oxygen quenchers like eugenol markedly reduce peroxidation. Membrane leakage of a similar rate is observed in light as well as in darkness. PA was described as a penetration enhancer intercalating with membranes. Our data corroborate that conclusion. Accordingly, the herbicidal mode of action of pelargonic acid is due first to membrane leakage in dark or light and second to peroxidation driven by radicals originating in the light by sensitized chlorophyll displaced from the thylakoids.     

杂草对9类常用不同作用机制除草剂的非靶标抗性机制研究进展

除草剂的应用为农业生产带来便利, 但长期、单一使用某一种或相同机制的除草剂也引发了杂草对除草剂的抗性问题。抗性杂草种类逐渐增加, 抗性形成机制复杂, 导致农田杂草的治理难度增加。杂草对除草剂的抗性机制主要分为两种, 一种是除草剂靶标位点基因的突变或过量表达导致的靶标抗性, 另一种是杂草对除草剂吸收、转运、固存和代谢等一个或多个生理过程发生变化导致的非靶标抗性。本文综述了杂草对9类不同作用方式除草剂的非靶标抗性机制的生理、生化和分子基础的研究进展, 以期为抗性杂草综合治理提供参考。     

Rationale for a natural products approach to herbicide discovery

Weeds continue to evolve resistance to all the known modes of herbicidal action, but no herbicide with a new target site has been commercialized in nearly 20 years. The so-called 'new chemistries' are simply molecules belonging to new chemical classes that have the same mechanisms of action as older herbicides (e.g. the protoporphyrinogen-oxidase-inhibiting pyrimidinedione saflufenacil or the very-long-chain fatty acid elongase targeting sulfonylisoxazoline herbicide pyroxasulfone). Therefore, the number of tools to manage weeds, and in particular those that can control herbicide-resistant weeds, is diminishing rapidly. There is an imminent need for truly innovative classes of herbicides that explore chemical spaces and interact with target sites not previously exploited by older active ingredients. This review proposes a rationale for a natural-products-centered approach to herbicide discovery that capitalizes on the structural diversity and ingenuity afforded by these biologically active compounds. The natural process of extended-throughput screening (high number of compounds tested on many potential target sites over long periods of times) that has shaped the evolution of natural products tends to generate molecules tailored to interact with specific target sites. As this review shows, there is generally little overlap between the mode of action of natural and synthetic phytotoxins, and more emphasis should be placed on applying methods that have proved beneficial to the pharmaceutical industry to solve problems in the agrochemical industry.     

The toxicity of herbicides to non-target aquatic plants and algae: assessment of predictive factors and hazard

Widely used herbicides sometimes inadvertently contaminate surface waters. In this study we evaluate the toxicity of herbicides to aquatic plants and algae and relate it to environmental herbicide concentrations and exposure scenarios, herbicide formulation and mode of action. This was done experimentally for ten herbicides, using the aquatic macrophyte Lemna minor L. and the green alga Pseudokirchneriella subcapitata (Korshikov) Hindak, supplemented with a database study comprising algae toxicity data for 146 herbicides. The laboratory study showed that herbicide formulations in general did not enhance herbicide efficacy in the aquatic environment. The Roundup formulation of glyphosate proved to be the only exception, decreasing the EC(50) of the technical product for both L. minor and P. subcapitata approximately fourfold. Comparison of the sensitivity of L. minor and P. subcapitata revealed up to 1000-fold higher sensitivity of L. minor for the herbicides categorized as weak acids (pK(a) < 5), emphasizing the importance of higher plants in hazard assessment. Database analyses showed that no herbicide group, categorized by site of action, was significantly more toxic than another. Synthetic auxins were the exception as they are virtually non-toxic to unicellular algae. There was no strong correlation between toxicity to algae and K(ow) of the herbicides, not even within groups having the same site of action. Evaluating all data, few herbicides were toxic at concentrations below 1 microg l(-1), which is the 99.9th percentile of the herbicide concentrations measured in the Danish surveillance programme. Joint action of several herbicides cannot however be excluded.     

嘧啶(氧)硫苯甲酸类除草剂研究进展

嘧啶(氧)硫苯甲酸类除草剂是超高效除草剂类型之一,是新一代绿色、安全、高效、低残留农药,具有很高的推广价值。本文综述了嘧啶(氧)硫苯甲酸类除草剂的主要类型、作用机理、国内外应用现状,总结了目前的研究进展;对其引发的杂草抗药性问题进行阐述。可为嘧啶(氧)硫酸苯甲酸类除草剂的农业应用及科学研究提供借鉴。