Diphenyl Ether Herbicides Research Articles

Effect of different weed management practices on growth, yield attributes and yield of direct seeded rice (Oryza sativa L.)

A field experiment was conducted on Instructional cum Research Farm, Indira Gandhi Krishi Vishwavidyalaya, Raipur (C.G.) during kharif season 2018 to evaluate the new formulation of oxyfluorfen (20 % DF) on weed control in direct seeded rice. Oxyfluorfen is a diphenyl-ether herbicide as a pre-emergence herbicide used for control of annual, perennial and broad leaved weeds in a various field crops. Pre-emergence (PE) application of oxyfluorfen 20 DF @ 720 g ha-1 gave significantly lower total weed density, weed dry weight and higher weed control efficiency at all the intervals. However, Oxyfluorfen 20 DF @ 240 g ha-1 as PE herbicide can keep the weed density and dry weight below the economic threshold level and increase the grain yield (49.51 q ha-1) and straw yield (64.52 q ha-1) in direct seeded rice. Unweeded control accounted for lower grain yield (5.83 q ha-1) which causes higher weed density and dry weight, respectively due to heavy competition of weeds for nutrients, space and light.

Aclonifen targets solanesyl diphosphate synthase, representing a novel mode of action for herbicides.

Aclonifen is a unique diphenyl ether herbicide. Despite its structural similarities to known inhibitors of the protoporphyrinogen oxidase (e.g. acifluorfen, bifenox or oxadiazon), which result in leaf necrosis, aclonifen causes a different phenotype that is described as bleaching. This also is reflected by the Herbicide Resistance Action Committee (HRAC) classification that categorizes aclonifen as an inhibitor of pigment biosynthesis with an unknown target. A comprehensive Arabidopsis thaliana RNAseq dataset comprising 49 different inhibitor treatments and covering 40 known target pathways was used to predict the aclonifen mode of action (MoA) by a random forest classifier. The classifier predicts for aclonifen a MoA within the carotenoid biosynthesis pathway similar to the reference compound norflurazon that inhibits the phytoene desaturase. Upon aclonifen treatment, the phytoene desaturation reaction is disturbed, resulting in a characteristic phytoene accumulation in vivo. However, direct enzyme inhibition by the herbicide was excluded for known herbicidal targets such as phytoene desaturase, 4-hydroxyphenylpyruvate dioxygenase and homogentisate solanesyltransferase. Eventually, the solanesyl diphosphate synthase (SPS), providing one of the two homogentisate solanesyltransferase substrate molecules, could be identified as the molecular target of aclonifen. Inhibition was confirmed using biochemical activity assays for the A. thaliana SPSs 1 and 2. Furthermore, a Chlamydomonas reinhardtii homolog was used for co-crystallization of the enzyme-inhibitor complex, showing that one inhibitor molecule binds at the interface between two protein monomers. Solanesyl diphosphate synthase was identified as the target of aclonifen, representing a novel mode of action for herbicides. © 2020 Society of Chemical Industry.

Assessment of hematological, hepato-renal, antioxidant, and hormonal responses of Clarias gariepinus exposed to sub-lethal concentrations of oxyfluorfen

Little is known about the effects of oxyfluorfen, a diphenyl ether herbicide, exposure on the African catfish (Clarias gariepinus) health. Consequently, the existing investigation was designed to highlight the impacts of oxyfluorfen exposure on C. gariepinus hematological indices, liver and kidney functions, reproductive hormones, and oxidative status. Furthermore, a consequent 10-day depuration period was adopted to evaluate the recovery of the disturbed indicators to normal values. In the first experiment, the 96-h lethal concentration 50 (LC50) of oxyfluorfen for C. gariepinus was determined using probit analysis. Next, in a second experiment, 180 healthy fish (average initial body weight: 164.23 ± 0.24) were randomly assigned to 4 experimental groups exposed to 0, 1/10, 1/8, or 1/5 96-h LC50 of oxyfluorfen. The hematological profile, hepatic enzymes, kidney damage byproducts, reproductive hormones, oxidative stress, and lipid peroxidation indicators together with acetylcholinesterase (AChE) content were assessed. A histopathological examination of the hepatic, renal, brain, and testicular tissues was accomplished. Moreover, the expression of the oxidative stress-related gene was carried out. The results showed that 96-h LC50 of oxyfluorfen for C. gariepinus was 11.698 mg/L. Exposure to sublethal levels of oxyfluorfen induced macrocytic hypochromic anemia, leukopenia, lymphopenia, monocytopenia, and eosinopenia. Also, a concentration-dependent increase in alanine transaminase, alkaline phosphatase, aspartate transaminase, urea, creatinine, catalase, and malondialdehyde was detected following oxyfluorfen exposure together with upregulation of catalase gene. But, significant concentration-dependent reductions in AChE, glutathione transferase, reduced to oxidized glutathione ratio, estradiol, and testosterone activities were recorded. These biochemical alterations were accompanied by pathological perturbations in hepatic, renal, brain, and testicular tissues. Following 10 days of recovery, only the hematological impairments were abolished. Conclusively, the herbicides oxyfluorfen could induce multiple negative impacts on C. gariepinus with oxidative stress as a probable underlying mechanism. Additionally, a recovery period of 10 days was not enough to restore these impairments.

Enantioseparation of the racemates of a number of pesticides on a silica-based column with immobilized amylose tris(3-chloro-5-methylphenylcarbamate)

We report here the results from studies on the high-performance liquid chromatographic HPLC enantioresolution of thirty different types of pesticides on the chiral silica-based column with immobilized amylose tris(3-chloro-5-methylphenylcarbamate (ACMPC) (CHIRALPAK IG-3) under polar-organic and reversed-phase conditions measured at 20 °C. The main objective was to explore diverse polar and aqueous-based eluents for use with a single column to obtain an enantioseparation of polar pesticides usually found in environmental matrices. These pesticides included phenoxy- and aryloxyphenoxypropionic acids, imidazolinones, and diphenyl-ether herbicides; acylanilides, triazoles, and pyrimidine fungicides; chlordane and pyrethroid insecticides; organophosphorus compounds; and some metabolites and precursors. We obtained improved chromatographic enantioresolutions for seventeen of these compounds in either the polar-organic or reversed-phase modes, including six pesticides whose enantioseparation is reported for first time through the use of these chromatographic modes.

Biochemical and physiological mode of action of tiafenacil, a new protoporphyrinogen IX oxidase-inhibiting herbicide

We conducted biochemical and physiological experiments to investigate the mode of action of tiafenacil (Terrad'or™), a new protoporphyrinogen IX oxidase (PPO)-inhibiting pyrimidinedione herbicide. Analysis of the half-maximal inhibitory concentration (IC50) against recombinant PPO enzymes from various plant species, including amaranth (Amaranthus tuberculatus), soybean (Glycine max), arabidopsis (Arabidopsis thaliana), and rapeseed (Brassica napus), showed that tiafenacil had an IC50 of 22 to 28 nM, similar to the pyrimidinedione herbicides butafenacil and saflufenacil and the N-phenylphthalimide herbicide flumioxazin. By contrast, tiafenacil exhibited 3- to 134-fold lower IC50 values than the diphenyl ether herbicides fomesafen, oxyfluorfen, and acifluorfen. Tiafenacil is non-selective and is herbicidal to both dicots and monocots, such as the weeds velvetleaf (Abutilon theophrasti), amaranth, and barnyardgrass (Echinochloa crus-galli) as well as the crops soybean, rapeseed, rice (Oryza sativa), and maize (Zea mays) at concentrations ranging from 1 to 50 μM. Treatment of plant tissue with tiafenacil in darkness resulted in the accumulation of protoporphyrin IX. Subsequent exposure to light increased the content of malondialdehyde and significantly decreased the Fv/Fm values of chlorophyll fluorescence. The results suggest that tiafenacil is a new PPO-inhibiting pyrimidinedione herbicide.

Use of a Mutated Protoporphyrinogen Oxidase Gene as an Effective In Vitro Selectable Marker System that Also Conveys in planta Herbicide Resistance in Sugarcane

Genetic engineering can be used to introduce economically important traits in sugarcane cultivars. Part of any transformation process involves the selection of genetically transformed cells. In this study, an efficient sugarcane in vitro selection system was developed using mutated protophorhyrinogen oxidase (PPO) genes as selectable markers. Two PPO genes, that encode proteins targeted either to the mitochondria or plastid, were isolated from tobacco and maize. Site-directed mutagenesis was used to alter the nucleotide sequence of these genes so that the resulting proteins are less sensitive to diphenylether type herbicides. Sugarcane callus was genetically transformed through particle bombardment with constructs allowing expression of either transgene, and putative transgenic calli were selected on fomesafen. It took approximately 4 weeks to select herbicide resistant calli clones on 10 mg/l fomesafen in the presence of light, which increased the selection pressure, and a further 8 weeks to regenerate resistant plantlets. PCR analysis confirmed that all regenerated putative transgenic sugarcane plants contained the transgene. All transgenic plants showed levels of herbicide resistance when planted in soil.

Detoxification of diphenyl ether herbicide lactofen by Bacillus sp. Za and enantioselective characteristics of an esterase gene lacE

A bacterial strain Za capable of degrading diphenyl ether herbicide lactofen was isolated and identified as Bacillus sp. This strain could degrade 94.8% of 50mgL−1 lactofen after 4days of inoculation in flasks. It was revealed that lactofen was initially hydrolyzed to desethyl lactofen, which was further transformed to acifluorfen, followed by the reduction of the nitro group to yield aminoacifluorfen. The phytotoxicity of the transformed product aminoacifluorfen to maize was decreased significantly compared with the lactofen. A gene lacE, encoding an esterase responsible for lactofen hydrolysis to desethyl lactofen and acifluorfen continuously, was cloned from Bacillus sp. Za. The deduced amino acid belonging to the esterase family VII contained a typical Ser-His-Asp/Glu catalytic triad and the conserved motifs GXSXG. The purified recombinant protein LacE displayed maximal esterase activity at 40°C and pH 7.0. Additionally, LacE had broad substrate specificity and was capable of hydrolyzing p-nitrophenyl esters. The enantioselectivity of LacE during lactofen degradation was further studied, and the results indicated that the (S)-(+)-lactofen was degraded faster than the (R)-(−)-lactofen, which could illustrate the reported phenomenon that (S)-(+)-lactofen was preferentially degraded in soil and sediment.

Biochemical characterization of an enantioselective esterase from Brevundimonas sp. LY-2

BackgroundLactofen, a member of the diphenylether herbicides, has high activity and is commonly used to control broadleaf weeds. As a post-emergent herbicide, it is directly released to the environment, and easily caused the pollution. This herbicide is degraded in soil mainly by microbial activity, but the functional enzyme involved in the biodegradation of lactofen is still not clear now.ResultsA novel esterase gene lacH, involved in the degradation of lactofen, was cloned from the strain Brevundimonas sp. LY-2. The gene contained an open reading frame of 921 bp, and a putative signal peptide at the N-terminal was identified with the most likely cleavage site between Ala 28 and Ala 29. The encoded protein, LacH, could catalyze the hydrolysis of lactofen to form acifluorfen. Phylogenetic analysis showed that LacH belong to family V of bacterial lipolytic enzymes. Biochemical characterization analysis showed that LacH was a neutral esterase with an optimal pH of 7.0 and an optimal temperature of 40 °C toward lactofen. Besides, the activity of LacH was strongly inhibited by Hg2+ and Zn2+. LacH preferred short chain p-nitrophenyl esters (C2–C6), exhibited maximum activity toward p-nitrophenyl acetate. Furthermore, the enantioselectivity of LacH during lactofen hydrolysis was also studied, and the results show that R-(−)-lactofen was degraded faster than S-(+)-lactofen, indicating the occurrence of enantioselectivity in the enzymatic reaction.ConclusionsOur studies characterized a novel esterase involved in the biodegradation of diphenylether herbicide lactofen. The esterase showed enantioselectivity during lactofen degradation, which revealed the occurrence of enzyme-mediated enantioselective degradation of chiral herbicides.

Determination of Diphenylether Herbicides in Water Samples Using Dispersive Liquid-Liquid Microextraction Combined with High-Performance Liquid Chromatography.

Shaker-assisted dispersive liquid-liquid microextraction (SA-DLLME) and surfactant dispersive liquid-liquid microextraction (SDLLME) have been developed to determine five diphenylether herbicides in water samples using high-performance liquid chromatography with photodiode array detection (HPLC-PDA). For SA-DLLME, an up-and-down shaker-assisted emulsification was used. Extraction was complete in 3 min. Only 30 μL of decyl acetate was required, without a dispersive solvent. The linear range was from 2 to 1000 μg L-1, the coefficient of determination (r2) was better than 0.9992, and the limit of detection (LOD) was from 0.62 to 1.74 μg L-1. The relative recovery (RR) ranged from 90 to 102% for river water, 88 to 104% for lake water, and 93 to 102% for irrigating water. In SDLLME, a microsyringe was used to withdraw and discharge a mixture consisting of an extraction solvent and 1 mg L-1 Tween 60 as a surfactant four times within 10 s to form an emulsified solution. The linear range for the target compounds was from 2 to 1000 μg L-1. The LODs were between 0.72 and 1.38 μg L-1. The RR ranged from 95 to 108% for river water, 96 to 109% for lake water, and 86 to 114% for irrigating water.

Characterization of a novel oxyfluorfen-degrading bacterial strain Chryseobacterium aquifrigidense and its biochemical degradation pathway.

Persistent use of the diphenyl ether herbicides oxyfluorfen may seriously increase the health risks and ecological safety problems. A newly bacterium R-21 isolated from active soil was able to degrade and utilize oxyfluorfen as the sole carbon source. R-21 was identified as Chryseobacterium aquifrigidense by morphology, physiobiochemical characteristics, and genetic analysis. Under the optimum cultural conditions (pH 6.9, temperature 33.4°C, and inoculum size 0.2gL(-1)), R-21 could degrade 92.1% of oxyfluorfen at 50mgL(-1) within 5days. During oxyfluorfen degradation, six metabolites were detected and identified by atmospheric pressure gas chromatography coupled to quadrupole-time of flight mass spectrometry and ultra-performance liquid chromatography coupled to quadrupole-time of flight mass spectrometry, and a plausible degradation pathway was deduced. Strain R-21 is a promising potential in bioremediation of oxyfluorfen-contaminated environments.

Early‐Season Lactofen Application has Limited Effect on Soybean Branch and Mainstem Yield Components

ABSTRACTRecent interest in maximizing soybean [Glycine max (L.) Merr.] yield has led producers to seek management strategies to affect soybean yield components. One strategy that has been pursued is application of diphenyl ether herbicides, such as lactofen, to early‐vegetative soybean to kill the apical meristem in an effort to increase soybean branching, resulting in increased node and pod numbers. The objective of this study was to determine if the application of lactofen and fomesafen herbicides can kill the soybean apical meristem and quantify how early‐season application of these herbicides affect soybean yield components. Field studies were established at two locations in Kentucky during the 2013 and 2014 growing seasons. Lactofen, fomesafen, leaf removal, and meristem removal treatments were applied to soybean at first, second, third, and fourth trifoliate stages. Plants were harvested at maturity and nodes, pods, and seeds per square meter and seed mass were determined for both mainstem and branches. Meristem removal increased soybean branch development and shifted yield component formation from the mainstem nodes to branch nodes. Lactofen and fomesafen had small and inconsistent effects on mainstem and branch yield components compared with untreated soybean but did not affect total yield components. Lactofen and fomesafen were not able to kill the apical meristem or increase branching in soybean. Attempting to increase soybean node number through agronomic management does not appear to be a viable strategy to increase soybean yield.

Characterization of PPO-Inhibitor–Resistant Waterhemp (Amaranthus tuberculatus) Response to Soil-Applied PPO-Inhibiting Herbicides

Waterhemp resistance to foliar applications of protoporphyrinogen oxidase (PPO)–inhibiting herbicides has become increasingly disconcerting given the widespread distribution of glyphosate resistance. Fortunately, soil-residual PPO-inhibiting herbicides remain efficacious in waterhemp populations resistant to PPO-inhibiting herbicides; however, these herbicides should theoretically select for the resistant biotype as herbicide concentrations diminish in the soil. Accordingly, the objectives of this research were twofold: (1) evaluate the efficacy of three PPO-inhibiting herbicides, foliar- and soil-applied, on PPO-resistant (PPO-R) and PPO-susceptible (PPO-S) waterhemp, and (2) investigate the differential effects of PPO-inhibiting herbicides on an R biotype and an S biotype during several discrete developmental events relevant to soil–residual herbicide activity (i.e., radicle protrusion, radicle elongation, and waterhemp emergence). Greenhouse and growth chamber experiments indicated that the R biotype was least sensitive to the diphenylether herbicide fomesafen, followed by sulfentrazone and flumioxazin; however, fomesafen pluss-metolachlor improved soil-residual efficacy over fomesafen alone. Growth stage considerably influenced the R : S ratio, decreasing from 38× to 3.4×, when comparing ratios generated from foliar applications and soil-residual applications measuring radicle protrusion, respectively. Overall, this research supports the use of full soil-residual herbicide rates, reinforcing the importance of best management practices to manage the spread of herbicide resistance.

Tobacco plants over-expressing the sweet orange tau glutathione transferases (CsGSTUs) acquire tolerance to the diphenyl ether herbicide fluorodifen and to salt and drought stresses

The glutathione transferases (GSTs) are members of a superfamily of enzymes with pivotal role in the detoxification of both xenobiotic and endogenous compounds. In this work, the generation and characterization of transgenic tobacco plants over-expressing tau glutathione transferases from Citrus sinensis (CsGSTU1 and CsGSTU2) and several cross-mutate forms of these genes are reported. Putative transformed plants were verified for the presence of the transgenes and the relative quantification of transgene copy number was evaluated by Taqman real time PCR. The analysis of gene expression revealed that transformed plants exhibit high levels of CsGSTU transcription suggesting that the insertion of the transgenes occurred in transcriptional active regions of the tobacco genome. In planta studies demonstrate that transformed tobacco plants gain tolerance against fluorodifen. Simultaneously, the wild type CsGSTU genes were in vitro expressed and their kinetic properties were determined using fluorodifen as substrate. The results show that CsGSTU2 follows a Michaelis–Menten hyperbolic kinetic, whereas CsGSTU1 generates a sigmoid plot typical of the regulatory enzymes, thus suggesting that when working at sub-lethal fluorodifen concentrations CsGSTU2 can counteract the herbicide injury more efficiently than the CsGSTU1. Moreover, the transgenic tobacco plant over-expressing CsGSTs exhibited both drought and salinity stress tolerance. However, as we show that CsGSTUs do not function as glutathione peroxidase in vitro, the protective effect against salt and drought stress is not due to a direct scavenging activity of the oxidative stress byproducts. The transgenic tobacco plants, which are described in the present study, can be helpful for phytoremediation of residual xenobiotics in the environment and overall the over-expression of CsGSTUs can be helpful to develop genetically modified crops with high resistance to abiotic stresses.

Effects of fomesafen on soil enzyme activity, microbial population, and bacterial community composition

Fomesafen is a diphenyl ether herbicide that has an important role in the removal of broadleaf weeds in bean and fruit tree fields. However, very little information is known about the effects of this herbicide on soil microbial community structure and activities. In the present study, laboratory experiments were conducted to examine the effects of different concentrations of fomesafen (0, 10, 100, and 500 μg/kg) on microbial community structure and activities during an exposure period of 60 days, using soil enzyme assays, plate counting, and denaturing gradient gel electrophoresis (DGGE). The results of enzymatic activity experiments showed that fomesafen had different stimulating effects on the activities of acid phosphatase, alkaline phosphatase, and dehydrogenase, with dehydrogenase being most sensitive to fomesafen. On the tenth day, urease activity was inhibited significantly after treatment of different concentrations of fomesafen; this inhibiting effect then gradually disappeared and returned to the control level after 30 days. Plate counting experiments indicated that the number of bacteria and actinomycetes increased in fomesafen-spiked soil relative to the control after 30 days of incubation, while fungal number decreased significantly after only 10 days. The DGGE results revealed that the bacterial community varied in response to the addition of fomesafen, and the intensity of these six bands was greater on day 10. Sequencing and phylogenetic analyses indicated that the six excised DGGE bands were closely related to Emticicia, Bacillus, and uncultured bacteria. After 10 days, the bacterial community exhibited no obvious change compared with the control. Throughout the experiment, we concluded that 0-500 μg/kg of fomesafen could not produce significant toxic effects on soil microbial community structure and activities.

Field dissipation of oxyfluorfen in onion and its dynamics in soil under Indian tropical conditions

Oxyfluorfen, a diphenyl-ether herbicide is being used to control annual and perennial broad-leaved weeds and sedges in a variety of field crops including onion. The present study was aimed to investigate the dynamics and field persistence of oxyfluorfen in onion plant, bulb and soil under Indian tropical conditions. Application of four rates of oxyfluorfen viz., 200, 250, 300 and 400 g AI ha−1 as pre-emergence gave good weed control in field experiment with onion. The oxyfluorfen residue dissipated faster in plant than in soil respectively, with a mean half-life of 6.1 and 11.2 days. Dissipation followed first-order kinetics. In laboratory column leaching experiments, 17 percent of the applied oxyfluorfen was recovered from the soil and indicates its solubility in water and mobility in sandy clay loam soil was low. A sorption study revealed that the adsorption of oxyfluorfen to the soil was highly influenced by the soil organic carbon with the Koc value of 5450. The study concludes that the dissipation of oxyfluorfen in soil and onion was dependent on the physico-chemical properties of the soil and environmental conditions.

Microbial Degradation of Fomesafen by a Newly Isolated Strain Pseudomonas zeshuii BY-1 and the Biochemical Degradation Pathway

Fomesafen is a diphenyl ether herbicide used to control the growth of broadleaf weeds in bean fields. Although the degradation of fomesafen in soils was thought to occur primarily by microbial activity, little was known about the kinetic and metabolic behaviors of this herbicide. This paper reported the capability of the newly isolated strain Pseudomonas zeshuii BY-1 to use fomesafen as the sole source of carbon in pure culture for its growth. Up to 88.7% of 50 mg of L(-1) fomesafen was degraded by this bacterium in mineral medium within 3 days. Strain BY-1 could also degrade other diphenyl ethers, including lactofen, acifluorfen, and fluoroglycofen. During the fomesafen degradation, five metabolites were detected and identified by liquid chromatography-mass spectrometry and tandem mass spectrometry. The primary degradation pathway of fomesafen might be the reduction of the nitro group to an amino group, followed by the acetylation of the amino derivative, dechlorination, and cleavage of the S-N bond. The addition of the BY-1 stain into soils treated with fomesafen resulted in a higher degradation rate than that observed in uninoculated soils, and the bacteria community in contaminated soil recovered after inoculation of the BY-1 stain. On the basis of these results, strain P. zeshuii BY-1 has the potential to be used in the bioremediation of fomesafen-contaminated soils.

Oxidative stress and lipid peroxidation in the earthworm Eisenia fetida induced by low doses of fomesafen

Formesafen is a diphenyl ether herbicide that has adverse effects on non-target animals. However, knowledge about the effect of fomesafen on the antioxidant defense system in earthworms is vague. Thus, it is essential to investigate the effects of fomesafen on the antioxidant defense system in earthworms as a precautionary method. In the present study, earthworms (Eisenia fetida) were exposed to artificial soil treated with a range of concentrations of fomesafen (0, 10, 100, and 500 μg kg(-1)) and were collected on the 3rd, 7th, 14th, 21st, and 28th days of exposure. Subsequently, the antioxidant enzyme activities (superoxide dismutase (SOD); catalase (CAT); and guaiacol peroxidase (POD)), reactive oxygen species (ROS) level, and malondialdehyde (MDA) content due to fomesafen treatment were examined in earthworms. Compared with the control, the SOD activity increased on the third and seventh days but decreased on the 14th day due to treatment with 100 and 500 μg kg(-1) of fomesafen. The activities of CAT and POD increased significantly on the third, seventh, and 14th days of exposure. In addition, the ROS level was significantly enhanced throughout the entire experimental period and showed a statistically dose-dependent relationship on the seventh and 14th days. The MDA content markedly increased on the seventh day of exposure; however, obvious changes were not detected at other exposure period. Low doses of fomesafen (≤ 500 μg kg(-1)) may result in oxidative damage and lipid peroxidation in E. fetida by inducing the generation of ROS at short exposure periods (14 days). However, the adverse effects of fomesafen gradually disappear as the cooperation of antioxidant enzymes and exposure time are prolonged. This result may be helpful for further studies on the toxicological mechanisms of fomesafen to earthworms.

Ameliorative effects of squash (Cucurbita moschata Duchesne ex Poiret) leaf extracts on oxidative stress

This study screened paraquat-tolerant plants among 10 plant species, including monocots and dicots angiosperms. Squash (Cucurbita moschata Duchesne ex Poiret) and kidney bean (Phaseolus vulgaris L.) plants exhibited the highest photooxidation-tolerant phenotypes upon a foliar treatment with paraquat. A foliar treatment with paraquat pre-mixed with leaf water extracts from the squash plant significantly alleviated paraquat-induced oxidative damage in maize, but this was not the case after a treatment with the hydrophobic phase of the leaf extracts. In particular, the water extract from young leaves (4th true leaf) of squash plants conferred tenfold higher tolerance to oxidative damage in paraquat-treated leave tissues compared to paraquat-only treatment. This tolerance was tightly linked not only to the increased amounts of ascorbic acid and dehydroascorbate antioxidants in the damaged leaves, but also to the reduced chlorophyll loss, lipid peroxidation, and cellular electrolyte leakage. Moreover, the protective effects of the water extract were apparent when using another bipyridyl herbicide, diquat, but not with a diphenyl-ether herbicide, oxyfluorfen. On the other hand, pre-treatment with the extract prior to the onset of drought or cold stress had no significant antioxidative effect on the treated tissues.

Morphological and physiological alterations induced by lactofen in soybean leaves are reduced with nitric oxide

Lactofen is a diphenylether herbicide recommended to control broad-leaved weeds in soybean (Glycine max) fields and its mechanism of action is the inhibition of protoporphyrinogen-IX oxidase (Protox), which acts in the chlorophyll biosynthesis. This inhibition results in an accumulation of protoporphyrin-IX, which leads to the production of reactive oxygen species (ROS) that cause oxidative stress. Consequently, spots, wrinkling and leaf burn may occur, resulting in a transitory crop growth interruption. However, nitric oxide (NO) acts as an antioxidant in direct ROS scavenging. Thus, the aim of this work was to verify, through phytometric and biochemical evaluations, the protective effect of NO in soybean plants treated with the herbicide lactofen. Soybean plants were pre-treated with different levels of sodium nitroprusside (SNP), a NO-donor substance, and then sprayed with 168 g a.i. ha-1 lactofen. Pre-treatment with SNP was beneficial because NO decreased the injury symptoms caused by lactofen in young leaflets and kept low the soluble sugar levels. Nevertheless, NO caused slower plant growth, which indicates that further studies are needed in order to elucidate the action mechanisms of NO in signaling the stress caused by lactofen in soybean crop.

The herbicide aclonifen: The complex theoretical bases of sunflower tolerance

Aclonifen is a diphenylether herbicide in which one ring is unsubstituted and the other is NH 2-1, Cl-2, NO 2-6 substituted. This substitution, especially NH 2-1, is a particular feature in the diphenylether herbicidal family. In contrast with other herbicides of the same family (acifluorfen, oxyfluorfen, bifenox) this compound is not only acting through a phytotoxic protoporphyrin IX accumulation but also through an inhibition of carotenoid biosynthesis. Both biochemical targets are associated to chloroplast structuration in young seedlings under light and the pre-emergence or preplant treatment is consequently an appropriate agronomic strategy. Numerous weeds such as Alopecurus sp., Sinapis sp., Brassica sp., Chenopodium sp. are very sensitive to this herbicide but sunflower culture appears very tolerant. Our results suggest that this tolerance has a complex origin including (1) low root uptake, (2) conjugation in the roots probably with glutathione and (3) low xylem transfer from root to shoot. The low root uptake is associated to aclonifen crystallization on the root surface at high concentrations. The combination of this physico-chemical effect with a sufficient root conjugation rate can explain both the very low amounts of aclonifen or derivatives found in the aerial parts and the strong sunflower tolerance.