Assessment of fungicide systemicity in wheat using LC-MS/MS

BACKGROUND: Systemicity is an important attribute of fungicides that is difficult to measure in early‐stage screening without labeling the compound with a radioisotope. A method of measuring translocation that does not require potent fungicidal activity or a radiolabel would guide identification of compounds with desirable attributes. RESULTS: The authors developed an analytical technique that mimics field application, using LC‐MS/MS to screen compounds for translocation in wheat leaves. The method sorted commercial and experimental fungicides appropriately into systemic and non‐systemic categories. A model using LC‐MS/MS data was equivalent to a lipophilicity model and superior to a water solubility model at predicting compound systemicity. CONCLUSION: Early‐stage compounds can be screened for systemicity on whole plants using LC‐MS/MS. Copyright © 2008 Society of Chemical Industry     

The influence of water solubility on the movement and degradation of simazine in a fallow soil

The movement and degradation of simazine in the field during winter and summer were measured and compared with simulations using a simple model. The model only simulated simazine behaviour closely when water solubility was taken into account. Relationships between water solubility, melting point, soil adsorption and octan-1-ol/water partition coefficient indicate that, at agricultural rates of application, water solubility will only have an important influence on behaviour for relatively polar chemicals with high melting points.     

Biological properties of the novel fungicide cyazofamid against Phytophthora infestans on tomato and Pseudoperonospora cubensis on cucumber

Cyazofamid (ISO proposed common name), 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide is a novel fungicide exhibiting specific activity against diseases caused by Oomycetes. In tests, cyazofamid at 0.4-1.6 mg litre-1 exhibited excellent preventative activity against Phytophthora infestans on tomato and Pseudoperonospora cubensis on cucumber. Minimum inhibitory concentrations of cyazofamid against both diseases were over 63 times lower than those of mancozeb and at least 16 times lower than those of metalaxyl. Cyazofamid at 1.6-25 mg litre-1 exhibited not only preventative activity, but also stable residual activity and rainfastness. Cyazofamid at 6.3 mg litre-1 reduced zoosporangia formation of P infestans and P cubensis on host plants by 100 and 94% respectively. Cyazofamid also exhibited translaminar and curative activity. Cyazofamid has a new mode of action for fungicides and exhibits no cross-resistance with other currently registered and commonly used fungicides. These properties lead to a high level control by cyazofamid in field.     

Translocation and translaminar bioavailability of two neonicotinoid insecticides after foliar application to cabbage and cotton

A laboratory study was undertaken to investigate the leaf systemic properties and the translaminar aphicidal activity of two commercialised neonicotinoid (chloronicotinyl) insecticides. For that purpose [14C]imidacloprid was subjected to uptake and translocation studies in cabbage and cotton after foliar application. Foliar penetration and short-term translocation patterns of imidacloprid were similar in both plant species. Nevertheless imidacloprid penetrated twice as much into cabbage leaves as it did into cotton leaves. It showed a comparable translaminar behaviour and was entirely translocated acropetally, indicating its well-known xylem mobility. The translaminar and acropetal movement of imidacloprid and acetamiprid were quantified by simple laboratory bioassays using the green peach aphid, Myzus persicae (Sulzer), and the cotton aphid, Aphis gossypii (Glover), as typical homopteran pests for cabbage and cotton, respectively. A single dose (7.5 micrograms AI per leaf) applied to the upper leaf surface of cabbage and cotton was tested against aphids feeding on the lower leaf surface both close to and distant from the site of application 1, 5 and 12 days after treatment. The translaminar residual activity of imidacloprid on cabbage leaves was superior to that of acetamiprid, whereas its translaminar efficacy against A gossypii on cotton was inferior to that of acetamiprid. However, oral ingestion bioassays using an artificial double membrane feeding system revealed no significant differences in intrinsic activity between the two neonicotinoids tested.     

嘧菌酯对扁豆纹枯病的物理作用方式及其生物动力学特性

以多菌灵和福美双为对照药剂,测定了嘧菌酯对立枯丝核菌Rhizoctonia solani的抑制活性,并用离体叶片法测定了嘧菌酯对该病原菌引起的扁豆纹枯病的物理作用方式及其生物动力学特性。嘧菌酯、多菌灵和福美双对立枯丝核菌菌丝生长的EC50值分别为0.072 4、1.134 4和1.202 6 μg/mL。施药后立即接种, 250 μg /mL嘧菌酯、500 μg /mL多菌灵和1 000 μg /mL福美双对扁豆纹枯病的保护效果分别为95.61％、99.88％和81.45％;施药3 d后再接种,嘧菌酯、多菌灵和福美双对扁豆纹枯病的保护效果分别为92.27％、100％和46.96％;接种36 h后再施药,3种药剂对扁豆纹枯病的治疗效果分别为90.40％、95.75％和61.94％。表明嘧菌酯对扁豆纹枯病具有很好的保护作用、持效性和治疗作用。在叶片基部施药后在顶部接种,嘧菌酯、多菌灵和福美双对扁豆纹枯病的防治效果分别为87.81％、42.09％和7.24％;在叶片背面施药后在正面接种,3种药剂对扁豆纹枯病的保护效果分别为87.30％、37.00％和16.15％。表明嘧菌酯在扁豆叶片中具有很好的木质部输导和跨层转移活性。     

Effects of some nonionic polyoxyethylene surfactants on uptake of ethirimol and diclobutrazol from suspension formulations applied to wheat leaves

The influence of a number of commercial nonionic polyoxyethylene surfactants on the foliar penetration and movement of two systemic fungicides, ethirimol and diclobutrazol, was studied in outdoor-grown wheat plants at different growth stages and post-treatment temperatures in two consecutive growing seasons. Both fungicides were applied as ca 0·2 μl droplets of aqueous suspension formulations containing 0·5 g litre^?1 of ¹⁴C-labelled active ingredient; surfactants were added to these suspensions at concentrations ranging from 0·2-10 g litre^?1. To achieve optimum uptake of each fungicide the use of surfactants with different physicochemical properties was required. For diclobutrazol, a lipophilic compound, uptake of radiolabel was best with surfactants of low mean molar ethylene oxide (E) content (5-6) but it was necessary to use concentrations of ca 5 g litre^?1 to attain this. The surfactant threshold concentration for uptake enhancement of radiolabel from ethirimol formulations (< 2 g litre^?1) was much lower than that for diclobutrazol but surfactants with E contents > 10 induced the greatest amount of uptake. For both fungicides, surfactants with an aliphatic alcohol hydrophobe were generally more efficient in promoting their uptake than those with a nonylphenol moiety. The sorbitan-based surfactant ‘Tween 20’ proved to be an effective adjuvant only for the ethirimol formulation; the uptake enhancing properties of the block copolymer ‘Synperonic PE/F68’ were weak. Uptake performance could not be related to the spreading properties of the respective formulations on the wheat leaf surface or to differences in solubilisation of the two fungicides by the surfactants. Although surfactants could substantially increase the amount of acropetal transport of radiolabel from both fungicides, none of those tested specifically promoted it; a constant proportion of the radioactive dose absorbed by a treated leaf was usually exported away from the site of application. The results are discussed in the light of current theories about the mode of action of surfactants as spray adjuvants.     

The influence of lipophilicity and formulation on the distribution of pesticides in laboratory-scale sediment/water systems

Pesticide reaching surface waters will be sorbed by sediment. This sorption process and the influence of pesticide formulation have been examined at 10 degrees C in small-scale systems having 2-cm depth of sediment and 8-cm overlying water stirred gently. Eight pesticides (triasulfuron, isoproturon, chlorotoluron, phenmedipham, difenoconazole, chlorpyrifos, pendimethalin and permethrin), spanning a range of physicochemical properties, were applied individually to the water. Sorption equilibrium was reached at between 15 and 30 days, the proportion of pesticide then in the sediment ranging from 20% for the acidic and therefore polar triasulfuron to 97% for the lipophilic permethrin; this behaviour was not influenced by formulation. Sorption coefficients measured in batch tests over 2 h gave good estimates of the equilibrium distribution. Some degradation was observed for all compounds over 90 days; for some compounds and formulations, enhanced degradation occurred after 20 to 60 days. It is concluded that lipophilicity is the chief determinant of pesticide distribution in sediment/water systems.     

Comparative efficacy of strobilurin fungicides against downy mildew disease of pearl millet

Three commercial formulations of strobilurins, viz., azoxystrobin, kresoxim-methyl, and trifloxystrobin were evaluated for their efficacy against pearl millet downy mildew disease caused by Sclerospora graminicola. In vitro studies revealed inhibition of S. graminicola sporulation, zoospore release, and zoospore motility at 0.1-2 μg ml⁻¹ of all the three fungicides. The fungicides were evaluated for phytotoxic effects on seed quality parameters and for their effectiveness against downy mildew disease by treating pearl millet by: (1) seed dressing, (2) seed dressing followed by foliar spray, and (3) also by foliar spray alone. The highest non-phytotoxic concentrations of 5, 10, and 10 μg ml⁻¹ for azoxystrobin, trifloxystrobin, and kresoxim-methyl, respectively, were selected for further studies. Under greenhouse conditions, these fungicides showed varying degrees of protection against downy mildew disease. Among the three fungicides, azoxystrobin proved to be the best by offering disease protection of 66%. Further, seed treatment along with foliar application of these fungicides to diseased plants showed enhanced protection against the disease to 93, 82, and 62% in treatments of azoxystrobin, kresoxim-methyl and trifloxystrobin respectively. Foliar spray alone provided significant increase in disease protection levels of 91, 79, and 59% in treatments of azoxystrobin, kresoxim-methyl, and trifloxystrobin, respectively. Disease curative activity of azoxystrobin was higher compared to trifloxystrobin and kresoxim-methyl. Tested fungicides showed weaker translaminar activity, as the disease inhibition was marginal when applied on adaxial leaf surface. Partial systemic activity of azoxystrobin was evident by root uptake, while trifloxystrobin and kresoxim-methyl showed lack of systemic action in pearl millet. A trend in protection against downy mildew disease similar to greenhouse results was evident in the field trials. Grain yield was significantly increased in all strobilurin fungicide treatments over control and maximum increase in yield of 1673 kg ha⁻¹ was observed in combination treatments of seed treatment and foliar spray with azoxystrobin.     

The relaxing effect of herbicidal degradation products on a molluscan smooth muscle

Derivates of anilines and phenols are released in soil after microbial or hydrolytical cleavage of many herbicides and certain fungicides. Some of these herbicides inhibit tonic contractions in a molluscan smooth muscle elicited by ACh. Similar relaxing properties can be proved for anilines, phenols, and cyclohexylamine. The ability to diminish the amplitudes of ACh contractions is referred to chlorine atoms as the electron withdrawing ligands associated with the aromatic moiety of the tested substances. The water solubility and particularly the partition coefficient between aequous solution and the biological membrane also seem to influence the inhibitory effectiveness taking the octanol-water partition coefficient as a basis for the membrane-water partition coefficient. Regarding these considerations, factors modulating the properties of both, herbicides or degradation products may be similar to those, which determine the ability of phenols, anilines, and other substances being effective as anesthetics or tranquilizers. It is concluded that the mechanism for the specific relaxation by herbicides and degradation products is localized in the muscle cell membrane.     

Adsorption of systemic pesticides on ground stems and in the apoplastic pathway of stems,as related to lignification and lipophilicity of the pesticides

The adsorption of five systemic fungicides (carbendazim, triadimefon, nuarimol, triarimol, and fenarimol) and one herbicide (fluometuron) on ground stems and in the apoplastic pathway of excised pepper, cotton, and bean stems was studied. Adsorption on ground and water extracted stems, as well as retention in the apoplast of excised stems, increased with the 1-octanol/water partition coefficients of the pesticides. Methylation of ground stems increased their adsorption capacity (carbendazim excluded), while extraction with organic solvents did not affect it. Woody stems adsorbed more of the pesticides than herbaceous ones. Binding of pesticides in the apoplastic pathway of stems seems to be related to their degree of lignification and to the lipophilicity of the pesticides.     

Control of black foot disease in grapevine nurseries

Black foot disease of grapevines is a decline and dieback disease caused by a soilborne pathogen complex including Cylindrocarpon liriodendri , C. macrodidymum , Campylocarpon fasciculare and Campyl. pseudofasciculare . These pathogens cause primary infections of roots and basal ends of grafted cuttings in nursery soils. Thirteen fungicides were screened in vitro for mycelial inhibition of these pathogens. Prochloraz manganese chloride, benomyl, flusilazole and imazalil were the most effective fungicides tested, and were subsequently included in semi-commercial field trials. Basal ends of grafted cuttings were dipped in various chemical and biological treatments prior to planting in open-rooted nurseries. Black foot pathogens were not isolated from grafted cuttings prior to planting. Additional treatments involved soil amendments with Trichoderma formulations and hot water treatment of dormant nursery grapevines. Field trials were evaluated after eight months. Isolations from uprooted plants revealed low levels of black foot pathogens in the roots of untreated control plants, and significantly higher levels in basal ends of rootstocks. The incidence of black foot pathogens, as well as that of Petri disease pathogens, was not significantly and/or consistently reduced by the majority of chemical or biological treatments. However, these pathogens were not isolated from uprooted plants that were subjected to hot water treatment. It is therefore recommended that hot water treatment of dormant nursery plants be included in an integrated strategy for the proactive management of these diseases in grapevine nurseries.     

Uptake by roots and translocation to shoots of two morpholine fungicides in barley

Despite being lipophilic, morpholine fungicides are systemic in plants. Such transport may be explicable by their protonation (pKa∽7·5) at the pH of plant compartments to yield the more polar cation. This behaviour might be a useful attribute to be incorporated into other classes of lipophilic pesticides. To understand quantitatively the behaviour of the morpholine fungicides, the uptake by roots and transport to shoots in barley of two such ¹⁴C-labelled compounds, dodemorph and tridemorph, were investigated using bathing solutions of differing pH. At pH 5, uptake and transport were small, but increased by approximately two orders of magnitude at pH 8. Tridemorph, the more lipophilic of the two compounds, was highly accumulated by roots at pH 8 and moderately translocated to shoots. In contrast, dodemorph was translocated to shoots at pH 8 with remarkable efficiency, moving into the xylem across the endodermis at 23 times the efficiency of water, though accumulation in roots was less than that of tridemorph. Behaviour at 24 h was largely similar to that at 48 h for both compounds, indicating that uptake and translocation are equilibrium processes maintained over time. Transport to shoots for each compound was directly proportional to the concentrations accumulated in the roots, except at low pH where partitioning into root solids became proportionately more important with such material not being directly available for transport to the xylem across the endodermis. Uptake and transport of these basic fungicides are explained in terms of their partitioning and of their accumulation in acidic plant compartments by ion trapping as the protonated form; this behaviour is discussed in relation to the pKa and lipophilicity of these compounds. © 1998 Society of Chemical Industry     

Evaluation of the systemic activity of simeconazole in comparison with that of other DMI fungicides

The systemic activity of simeconazole (RS-2-(4-fluorophenyl)-1-(1H-1,2,4-triazol-1-yl)-3-trimethylsilylpropan-2-ol) in plants was compared with those of eight other sterol demethylation inhibitor (DMI) fungicides. Simeconazole prevented the infection of Blumeria graminis (DC) Speer f sp hordei Marchal on barley leaves within a radius of several centimeters from the edge of local treatment on the leaves when the compound was separated from the leaves by glass coverslips. This reveals that simeconazole has prominent vapour-phase activity. Simeconazole showed excellent curative activity against barley powdery mildew when treated 1-3 days after inoculation. Furthermore, this indicates that simeconazole has notable translaminar activity because, when the compound was applied onto either the adaxial or abaxial leaf surface, it showed excellent efficacy against powdery mildew on the opposite side of the leaf surface of barley and cucumber. Simeconazole also showed excellent efficacy against barley powdery mildew by soil drench 24h after inoculation. This suggests that simeconazole was absorbed very quickly into the barley plant after treatment. The permeability of the compound through cuticular membranes prepared from tomato fruits was about 20% at 22 h after the treatment and was much superior to that of the other DMI fungicides tested.     

保水剂对土壤的物理性质与水分入渗的动态影响

保水剂在农业上的应用对于缓解干旱具有重要的意义,但其应用后会发生降解而最终失去保水作用,因此了解其在降解过程中引起的土壤物理性质的动态变化及水分运动的机理,是其能否正确应用的关键,本试验以保水剂在农业应用中的典型用量为基础,研究了保水剂对土壤的物理性质动态影响及一维土壤水分。结果表明,保水剂施入土壤后其性能不断衰减是导致土壤物理性质不断变化的最根本原因;土壤中施用保水剂后土壤的质量饱和含水率明显增加,饱和导水率降低,但随着保水剂性能的逐渐衰减,饱和含水率呈现下降趋势,饱和导水率呈现上升趋势;施入保水剂后土壤的扩散率是一个曲面,并且随着保水剂自身性能的衰减,呈现逐渐扩展的趋势;施用保水剂后土壤入渗的湿润锋前进速度下降,这主要是由于施用保水剂土壤的饱和含水量增加和保水剂膨胀堵塞土壤孔隙造成的;通过对施用保水剂土壤的扩散率和导水率的分时段研究,最终建立施用保水剂土壤的一维水分运动方程,试验证明其可行,且精度在允许的范围内。     

A Field Test of Root Zone Water Quality Model—Pesticide and Bromide Behavior

The Root Zone Water Quality Model (RZWQM) is a process-based model developed recently by USDA–ARS scientists. The model integrates physical, chemical and biological processes to simulate the fate and movement of water and agrochemicals over and through the root zone at a representative point in a field with various management practices. The model was evaluated using field data for the movement of water and bromide, and the transformation and transport of cyanazine and metribuzin in the soil profile. The model reasonably simulated soil water and bromide movement. Pesticide persistence was predicted reasonably well using a two-site sorption model that assumes a rate-limited (i.e. long-term) adsorption–desorption process with the additional assumption of negligible degradation of inter-aggregate adsorbed pesticides.     

Factors influencing entry of pesticides into soil water

Leaching of pesticides and hence the risk of contamination of ground-water depends on the physicochemical properties of the pesticide, the properties of the soil and the weather. Lipophilicity is the most important physicochemical property influencing the movement of un-ionised pesticides through soil. Water solubility is usually only an important factor in leaching for a few moderately polar solids with high melting points. Organic matter content is the most important property of the soil for un-ionised pesticides whilst the mobility of weak acids depends on soil pH. Permanent anions and weak acids can be very weakly adsorbed and hence might easily reach groundwater. Applications in autumn are more likely to reach groundwater than those in spring because soil temperatures are low and rainfall exceeds evaporation in winter, enabling mobile pesticides to penetrate to subsoils where degradation rates can be very slow. Concentrations of pesticide in water entering subsoils cannot be reliably simulated to an accuracy of better than an order of magnitude because the complex patterns of water flow and the slow diffusion processes of the pesticide are insufficiently understood. The consequences of applying a mobile pesticide to soil where drainage is impeded or where the water table is near the surface need to be anticipated before it is registered for treatment of the soil.     

Uptake of chemicals from foliar deposits: Effects of plant species and molecular structure

The uptake from foliar deposits of 10 ¹⁴C-labelled compounds into each of 10 species of field-grown plants was measured 26 h after deposition by combustion of leaf tissue after removal of surface deposits. The compounds, which included eight pesticides, covered a wide range of lipophilicity and each was formulated in the same way; they were applied as droplets with a microsyringe. Uptake varied greatly between the species. All compounds were taken up well into maize and Xanthium pennsylvanicum, whereas relatively little entered the leaves of apple or orange. Uptake into the six other species varied according to the compound. Amongst the eight non-polar compounds, no relationship between the rate of uptake and molecular size was discerned, and only in X. pennsylvanicum was uptake related to the partition coefficient and water solubility. Considering all the compounds, weak relationships were observed between molecular cross-sectional area and uptake into four species. The range of the uptake rates (×130) was small compared with those of octan-1-ol-water partition coefficients (×10¹⁰) and water solublities (×10⁷) shown by the 10 compounds. Possible reasons for the absence of correlations between the uptake and the molecular properties considered are discussed. The results are consistent with either separate routes of cuticular entry for non-polar and polar compounds, or a common route for both types of compound. The generally poor uptake by apple and orange leaves, which may be related to their thick cuticles, highlights the need to develop special formulations to optimise uptake into these species.     

Fungicide modes of action and resistance in downy mildews

Among oomycetes, Plasmopara viticola on grape and Phytophthora infestans on potato are agronomically the most important pathogens requiring control measures to avoid crop losses. Several chemical classes of fungicides are available with different properties in systemicity, specificity, duration of activity and risk of resistance. The major site-specific fungicides are the Quinone outside inhibitors (QoIs; e.g. azoxystrobin), phenylamides (e.g. mefenoxam), carboxylic acid amides (CAAs; e.g. dimethomorph, mandipropamid) and cyano-acetamide oximes (cymoxanil). In addition, multi-site fungicides such as mancozeb, folpet, chlorothalonil and copper formulations are important for disease control especially in mixtures or in alternation with site-specific fungicides. QoIs inhibit mitochondrial respiration, phenylamides the polymerization of r-RNA, whereas the mode of action of the other two site-specific classes is unknown but not multi-site. The use of site-specific fungicides has in many cases selected for resistant pathogen populations. QoIs are known to follow maternal, largely monogenic inheritance of resistance; they bear a high resistance risk for many but not all oomycetes. For phenylamides, inheritance of resistance is based on nuclear, probably monogenic mechanisms involving one or two semi-dominant genes; resistance risk is high for all oomycetes. The molecular mechanism of resistance to QoIs is mostly based on the G143A mutation in the cytochrome b gene; for phenylamides it is largely unknown. Resistance risk for CAA fungicides is considered as low to moderate depending on the pathogen species. Resistance to CAAs is controlled by two nuclear, recessive genes; the molecular mechanism is unknown. For QoIs and CAAs, resistance in field populations of P. viticola may gradually decline when applications are stopped.     

杀菌剂混剂的增效作用

作用机制不同或相同的杀菌剂混合后能产生增效作用的理论与实践是开发新的杀菌剂混剂的基础。本文讨论了杀菌剂混剂增效作用的评价方法，不同类型杀菌剂混合后的增效作用，混剂在个体和群体水平下的增效作用以及杀菌剂混剂增效作用的机制，为杀菌剂混剂的开发提供理论依据。     

Additive and synergistic antifungal effects of copper and phenolic extracts from grape cane and apples

Background

Organic viticulture seeks sustainable alternatives for eco-toxic copper fungicides to control downy mildew caused by Plasmopara viticola. (Poly)phenol-rich extracts of agricultural byproducts are known to possess antifungal activity, but high production costs often limit their actual implementation.

Results

We developed and produced novel ligninsulfonate-based grape cane extract (GCE) formulations and an apple extract on a pilot plant scale, including a detailed (poly)phenol characterization by high-performance liquid chromatography photodiode array mass spectrometry (HPLC-PDA-MS). Our GCE formulations alone reduced downy mildew disease severity in greenhouse trials by 29%–69% in a dose-dependent manner, whereas a standard application of the copper-based agent alone reached ~56%. When applied together, disease severity was diminished by 78%–92%, revealing a synergistic effect that depended on the mixture ratio. Combining GCE formulations with the apple extract, additive effects were found (80% disease severity reduction).

Conclusion

The studied plant extracts are proposed to both substitute for and synergistically reinforce copper fungicides in grapevine downy mildew control. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.