Metolachlor influence on growth and terpenoid synthesis

Height and fresh weight of sorghum (Sorghum bicolor L. var GA 522 DR) grown in sand were reduced by metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide) (0, 0.125, 0.25, 0.5, or 1 ppmw) applied preemergence. Significantly different responses were obtained from plants grown at two light intensities (270 and 27 μein/m²/sec). When grown in nutrient solution containing 0, 0.0156, 0.0625, 0.25, 1, 16, or 64 ppmw metolachlor, shoot and root lengths were inhibited by metolachlor; fresh and dry weights of shoot, root, and total plant decreased as metolachlor concentration increased. Carotene content (micrograms per gram fresh weight) in sorghum leaves was decreased by metolachlor. Specific activity of carotene synthesized from [2-¹⁴C] mevalonic acid by carrot (Daucus carota L.) disks was reduced 50% by 10^?5 and 10^?4M metolachlor. Thus, terpenoid biosynthesis is influenced by metolachlor. Gibberellins are terminal products of plant terpenoid biosynthesis, and GA₃ reverses metolachlor inhibition of growth at specific ratios of GA₃ and metolachlor but not at other concentrations. Thus, one effect of metolachlor on plants may be an inhibition of GA synthesis that results in shoot and root growth reductions as metolachlor concentration increases. Other growth responses of plants to metolachlor are unexplained.     

Effect of herbicide antidotes on glutathione content and glutathione S-transferase activity of sorghum shoots

The effects of the herbicide antidotes CGA-92194 (α-[(1,3-dioxolan-2-yl-methoxy)-imino]benzeneacetonitrile), flurazole [phenylmethyl 2-chloro-4-(trifluoromethyl)-5-thiazolecarboxylate], dichlormid (2,2-dichloro-N,N-di-2-propenylacetamide), and naphthalic anhydride (1H,3H-naphtho(1,8-cd)-pyran-1,3-dione) on nonprotein thiol content, glutathione content, and glutathione S-transferase (GST) activity in etiolated sorghum (Sorghum bicolor L.) Moench) shoots were examined. CGA-92194 and naphthalic anhydride had no effect on nonprotein thiol or reduced glutathione (GSH) content of sorghum shoots. In contrast, dichlormid and flurazole increased nonprotein thiol content of sorghum shoots by 24 and 48%, respectively. These increases were largely attributable to an increase in GSH. The antidotes increased GST activity less than twofold when using CDNB (1-chloro-2,4-dinitrobenzene) as a substrate. In contrast, when using metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] as a substrate, the increase in GST activity in response to antidote treatment was much greater: flurazole (30-fold), CGA-92194 (20-fold), naphthalic anhydride (17-fold), dichlormid (5-fold). The degree of protection from metolachlor injury conferred by a particular antidote was strongly correlated (R² = 0.95) with its ability to enhance GST activity, as evaluated with metolachlor as substrate. A comparison of GST activity in untreated and CGA-92194-treated seedlings, over a range of metolachlor concentrations (0.5–500 μM), indicated that the relative enhancement of enzyme activity by CGA-92194 was greater at lower metolachlor concentrations. The rate of nonenzymatic conjugation of metolachlor and GSH in vitro was much less (on a gram fresh weight equivalent basis) than the enzymatic rate. These results are consistent with the hypothesis that the above antidotes protect sorghum by enhancing GST activity which results in accelerated detoxification of metolachlor via GSH conjugation.     

Effects of N, P and K on Striga asiatica (L.) Kuntze seed germination and infestation of sorghum

Sorghum (Sorghum bicolor (L.) Moench) plants were grown in pots with 12.5 and 50 mg applied N kg^?1 soil. With an increase of soil N, the Striga asiatica (L.) Kuntze infestation, as well as the sorghum shoot dry matter losses due to infestation, decreased. The relative differences in stimulant capacity to induce Striga seed germination among the four sorghum genotypes were not consistent over the 0 to 150 mg N 1^?1 range. The sorghum root exudate was considerably more active at 0 mg N 1^?1, than at 30 mg N 1^?1, and the stimulant produced at 150 mg N 1^?1 failed to induce Striga seed germination. Presence of N in the growth medium considerably reduced the effectiveness of the stimulating substance produced by sorghum roots, whereas K promoted stimulant activity only in the absence of N. The presence or absence of P in the growth medium did not affect Striga seed germinability, probably due to the inability of this element to interfere with the production or activity of the stimulating substance from the host plants. It can be concluded, therefore, that sorghum plants seem to produce active root exudate only in conditions of N deficiency.     

Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] inhibition of gibberellin precursor biosynthesis

[2-¹⁴C]Mevalonic acid incorporation into gibberellic acid precursors was measured in cell-free extracts from sorghum [Sorghum bicolor (L.) Moench var. G-522 DR] coleoptiles. ¹⁴C incorporation into ent-kaur-16-ene was inhibited ca. 90% by 10^?7 to 10^?4M metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide]. [¹⁴C]Geranylgeraniol (GG) content increased. [¹⁴C]Farnesol content was not altered and [¹⁴C]geraniol content decreased. Total ¹⁴C incorporation was decreased by metolachlor. In the safener [α-(cyanomethoximino)benacetonitrile]-treated sorghum seed coleoptile cell-free system, total ¹⁴C incorporation increased, [¹⁴C]kaurene and relative kaurence content increased 4× up to 10⁵M metolachlor, and [¹⁴C]farnesol, and [¹⁴C]GG contents increased while relative farnesol and relative GG contents were not influenced by metolachlor. Thus, the inhibition of kaurene synthesis by metolachlor was reversed by the safener. Since the biosynthetic processes are mevalonic acid → geraniol → farnesol → GG → copalylol → kaurene, these data corroborate a proposed gibberellic acid biosynthesis inhibition between GG and kaurene as well as a partial blockage between mevalonic acid and geraniol. Thus, a portion of metolachlor-induced growth inhibitions of sorghum could be explicable on the basis of gibberellic acid biosynthesis inhibitions.     

Ascorbic Acid Enhances Growth and Yield of Sweet Peppers (Capsicum annum) by Mitigating Salinity Stress

Salinity is a crucial problem which has affected crop productivity globally. Ascorbic acid is considered helpful against abiotic stresses due to its powerful antioxidant potential. In the pot experiment, salinity stress (0, 35, 70, and 105?mM) was applied to sweet peppers in split doses after 20 days of transplantation. To mitigate the adverse effects of salinity, ascorbic acid (0, 0.40, 0.80, and 1.20?mM) was applied as foliar spray after a 6-day interval during vegetative growth. Sweet pepper plants sprayed with distilled water (control) recorded maximum plant height (cm), leaf area (cm²), number of branches, stem diameter (mm), number of fruit plant^?1, fruit diameter (cm), yield plant^?1 (g), and chlorophyll content (mg 100?g^?1), while the maximum polyphenol oxidase (PPO) activity (unit mg protein^?1 min^?1) and ascorbate peroxidase (APX) activity (unit mg protein^?1 min^?1) were recorded in plants treated with 70?mM NaCl application. Salinity stress beyond 70?mM significantly reduced all the studied parameters. An ascorbic acid concentration of 1.20?mM significantly mitigated the negative effects of salt stress and recorded maximum plant height (cm), number of leaves plant^?1, leaf area (cm²), number of branches plant^?1, stem diameter (mm), number of fruit plant^?1, fruit diameter (cm), yield plant^?1 (g), chlorophyll content (mg 100?g^?1), PPO activity (unit mg protein^?1 min^?1), and APX activity (unit mg protein^?1 min^?1). Hence, a 1.20?mM concentration of foliar ascorbic acid could be used in saline conditions up to 70?mM of sodium chloride (NaCl) for better growth, productivity, and enzymatic activity of sweet peppers.

     

The role of waxes in the uptake of metolachlor into sorghum in relation to the protectant CGA 43089

The grass weed herbicide metolachlor (2-chloro-N-[2-ethyl-6-methylphenyl]-N-[2-methoxy-1-methylethyl]acetamide) which is especially effective against wild millets, inhibits the formation of epicuticular waxes on sorghum leaves. The metolachlor protectant CGA 43089 [α - (cyanomethoximino) - benzacetonitrile] prevents the depletion of the waxes on the leaves of metolachlor-treated sorghum plants, as demonstrated by scanning electron microscopy. This alteration of the plant surface polymers also changes their permeability to the herbicide. ¹⁴C-metolachlor uptake into isolated coleoptiles and first leaves of sorghum which had been pretreated with the herbicide was increased. Incubation with added protectant reduced the uptake of ¹⁴C-metolachlor. It is postulated that the modifications caused by metolachlor and its protectant to sorghum surface structures influence the action of the herbicide in two ways:

• 1 The selectivity observed against sorghum and millet grasses could occur because of an increased uptake of metolachlor through cuticles which are particularly sensitive to the structural changes caused by the herbicide, since the composition of the plant waxes is very species-specific.
• 2 The loss of cuticular integrity is prevented by the protectant CGA 43089, which greatly reduces penetration of metolachlor.

     

Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

Mesotrione control and pigment concentration of large crabgrass (Digitaria sanguinalis) under varying environmental conditions

BACKGROUND: Mesotrione is a carotenoid biosynthesis‐inhibiting herbicide currently labeled for crabgrass (Digitaria spp.) control. Mesotrione control of large crabgrass has been reported to vary with temperature and relative humidity; however, the effect of irradiance on mesotrione efficacy has not previously been reported. Likewise, little is known about pigment concentrations of Digitaria spp. The present research investigated the effects of mesotrione on large crabgrass, Digitaria sanguinalis (L.) Scop., control and pigment concentrations under varying irradiance at three temperatures. RESULTS: Mesotrione (0.28 kg ha^?1) control of large crabgrass did not differ between temperature levels (18, 26 and 32 °C). Control was similar at tested irradiance levels (600, 1100 and 1600 µmol m^?2 s^?1). Mesotrione reduced large crabgrass chlorophyll a, chlorophyll b and total carotenoid concentrations, as well as chlorophyll a to b ratios. Treated plant bleaching was highest 7 days after treatment (DAT) but decreased by 21 DAT. Treated plants were less than 10% necrotic 3 and 7 DAT but nearly 35% necrotic 21 DAT. Treated large crabgrass bleaching was highest and photochemical efficiency was lowest 7 DAT. These results indicate that some plant recovery occurs prior to 21 DAT. CONCLUSION: Although mesotrione efficacy has previously been reported to vary according to environmental factors, mesotrione control of large crabgrass did not vary with measured temperature and irradiance levels in this study. On account of crabgrass convalescence, secondary applications of mesotrione may control large crabgrass more effectively when applied prior to 21 DAT. Copyright © 2009 Society of Chemical Industry     

Cholinesterase inhibition by methamidophos and its subsequent reactivation

Methamidophos (O,S-dimethylphosphoramidothioate, Monitor) is an organophosphorus, cholinesterase-inhibiting insecticide. The rate constant (k_i) for inhibiting rat plasma cholinesterase (ChE) was 1.57 ± 0.03 × 10³M^?1 min^?1, for rat erythrocyte ChE was 8.86 ± 1.10 × 10³M^?1 min^?1, and for rat brain ChE was 6.58 ± 0.42 M^?1 min^?1. Brain and plasma cholinesterases spontaneously recovered from over 90% inhibition at 30 min to 50% inhibition in 4 and 14 hr, respectively. Pralidoxime increased the rate of reactivation in vitro. In vivo, rats poisoned with methamidophos exhibited signs of cholinergic stimulation. The LD₅₀ of ip methamidophos in male rats was 15 ± 0.7 mg/kg. Pralidoxime (60 mg/kg) and atropine (10 mg/kg) given with the methamidophos increased the LD₅₀ to 52 ± 4.9 mg/kg and 60 ± 0.4 mg/kg, respectively. In rats given 12.5 mg methamidophos (an LD₂₀), ChE activity was depressed 95 ± 12.5% in plasma, 92 ± 0.6% in stomach, and 88 ± 1% in brain at 1 hr after injection. At 48 hr after injection ChE activity had returned to 60% or more of control values in each of the tissues. Administration of a single dose of 60 mg/kg of pralidoxime along with methamidophos did not increase ChE activities at the times and places it was measured.     

Contribution of militarine and dactylorhin A to the plant growth‐inhibitory activity of a weed‐suppressing orchid,Bletilla striata

The methanol extract of Bletilla striata, an ornamental orchid in eastern Asia, exhibited plant growth‐inhibitory activity. It was purified by continuous chromatography, based on the inhibitory activity against the growth of lettuce seedlings, resulting in two glycosidic compounds, militarine and dactylorhin A. The EC₅₀ values of militarine and dactylorhin A against the radicle elongation of the lettuce seedlings were 0.28 and 0.88 mmol L^?1, respectively. The amount of militarine and dactylorhin A in the methanol extract of the aerial part of B. striata was calculated to be 5.6 and 7.5 mg g^?1 fresh weight, respectively. The inhibitory activity of militarine and its content in the methanol extract revealed that the plant growth‐inhibitory activity of the extract of B. striata was mainly related to militarine. The inhibitory activity of militarine against the growth of Italian ryegrass and timothy were of the same level as that of lettuce.     

Monitoring of resistance to spirodiclofen and five other acaricides in Panonychus citri collected from Chinese citrus orchards

BACKGROUND: Citrus red mite, Panonychus citri (McGregor), is one of the most important pesticide‐resistant pests in China. In order better to understand its resistance status, six populations of the mite were collected from Chinese citrus orchards for monitoring of resistance to spirodiclofen and another five acaricides. RESULTS: All the samples collected in the field in 2006 were susceptible to spirodiclofen. However, the LC₅₀ values in populations sampled in 2009 ranged from 3.29 to 418.24 mg L^?1 spirodiclofen, a 127‐fold difference between the least and most sensitive populations. Compared with a susceptible strain, 50‐fold and 90.8‐fold resistance to spirodiclofen was detected in populations sampled from Pinghe and Fuzhou in 2009, as well as cross‐resistance to spirotetramat. The LC₅₀ values for abamectin, fenpropathrin, hexythiazox and pyridaben in the collected samples ranged from 0.041 to 3.52 mg L^?1, from 23.91 to 696.16 mg L^?1, from 13.94 to 334.19 mg L^?1 and from 48.90 to 609.91 mg L^?1 respectively. CONCLUSION: Great variations in resistance to the tested acaricides were observed among the sampled populations. The Pinghe population developed resistance to all the acaricides tested. The Jianning population was susceptible to most acaricides tested, except pyridaben. Resistance management strategies were conducted on the basis of these observations. Copyright © 2010 Society of Chemical Industry     

Grain protectants for the control of malathion-resistant insects in stored sorghum

Duplicate experiments were carried out on bulk sorghum stored in South Queensland and in Central Queensland. Bioassays of treated grain, conducted during 6 months' storage, established that fenitrothion (12 mg kg^?1)+ bioresmethrin (1 mg kg^?1), and pirimiphos-methyl (4 mg kg^?1)+ carbaryl (8 mg kg^?1), controlled typical malathionresistant strains of Sitophilus oryzae (L.), Rhyzopertha dominica (F.), Tribolium castaneum (Herbst), and Ephestia cautella (Walker). Chlorpyrifos-methyl (10 mg kg^?1)+ pyrethrins (1.5 mg kg^?1)+ piperonyl butoxide (12 mg kg^?1), and fenitrothion (12 mg kg^?1)+ (1R)-phenothrin (1 mg kg^?1), also controlled the strains of S. oryzae, T. castaneum and E. cautella, but were only partly effective against R. dominica. Methacrifos (15 mg kg^?1) controlled all the tested species except E. cautella. Chemical assays established that the residues and rates of breakdown of these grain protectants on sorghum conformed to the general pattern for other cereal grains; residues from the above treatments were below the individual Maximum Residue Limits recommended by the Codex Alimentarius Commission.     

Nematicidal efficacy of MCW‐2, a new nematicide of the fluoroalkenyl group,against the root‐knot nematode Meloidogyne javanica

BACKGROUND: The small number of available nematicides and restrictions on the use of non‐fumigant nematicides owing to high toxicity to human and non‐target organisms hinder effective nematode control. The nematicidal efficacy of MCW‐2, a new nematicide of the fluoroalkenyl group, was evaluated against the root‐knot nematode Meloidogyne javanica (Treub.) Chitwood. RESULTS: MCW‐2 showed irreversible nematicidal activity against second‐stage juveniles of M. javanica in vitro, following exposure for 48 h at concentrations as low as 0.5 mg L^?1, in contrast to fenamiphos or cadusafos. When exposed to MCW‐2 for shorter periods, motile juveniles became immobile with time after rinsing in water. MCW‐2 at 8 mg L^?1 inhibited nematode hatching, which, however, recovered after rinsing in water. In pot and plot experiments, 0.5 mg MCW‐2 L^?1 soil and 2 kg MCW‐2 ha^?1, respectively, controlled M. javanica similarly to or better than fenamiphos or cadusafos at the same concentrations or at their recommended doses. In the soil, the nematicidal activity of MCW‐2 was less persistent than that of fenamiphos. CONCLUSION: MCW‐2 has potential to be used as a new non‐fumigant nematicide that probably has a novel mode of action. Copyright © 2009 Society of Chemical Industry     

Allelopathy and the active metabolites of the endophytic fungus,Alternaria J46, from Platycladus orientalis

The endophytic fungus, Alternaria J46, was isolated from the stem of the medicinal plant, Platycladus orientalis. A suspension of Alternaria J46 mycelial segments and the culture filtrates of the fungi exhibited marked seed germination inhibition against the monocot wheat, large crabgrass, bromegrass, rice and barnyardgrass and weak inhibition against the dicot redroot pigweed and morning glory, but it was safe for use on soybean, rape, cucumber, tomato, lettuce and radish crops. It is possible to use J46 culture filtrates in order to prevent monocot weeds in dicot cropland. Three active metabolites were isolated from an extract of the fungus cultures and elucidated as 3‐acetyl‐5‐sec‐butyltetramic acid (1, tenuazonic acid), 3‐acetyl‐5‐iso‐butyltetramic acid (2, vivotoxin II) and cyclo‐(L‐leucyl‐L‐proline) (3). Among these three compounds, compounds 1 and 2 showed significant phytotoxic effects on the seed germination of large crabgrass, while compound 3 exhibited weak activity, and all were safe for lettuce at 100 μg mL^?1. Accordingly, compounds 1 and 2 were the main active metabolites that were responsible for endophytic fungus Alternaria J46's strong seed germination inhibition against monocotyledons.     

Identification of new limonoids from Swietenia and their biological activity against insects

BACKGROUND: Natural limonoids are one group of compounds being studied for their insecticidal properties. To discover new limonoids with better activities, analogs were prepared via acylation and hydrolysis, and bioassayed. RESULTS: Analogs were identified using one‐ and two‐dimensional (COSY, HMQC and HMBC) ¹H and ¹³C NMR, IR and MS. 3‐O‐Isovalerylswietenolide (13) and 3‐O‐isobutyrylswietenolide (14) showed excellent antifeedant activity, with DC₅₀ values of 0.19 and 0.009 mg L^?1 respectively, compared with the natural limonoid swietenolide (80.6 mg L^?1) against fourth‐instar Spodoptera frugiperda (JE Smith) larvae. CONCLUSION: This work shows that limonoid analogs prepared through semi‐synthesis can be used as lead compounds for the development of new insecticides. Copyright © 2010 Society of Chemical Industry     

Effect of Candidatus Liberibacter asiaticus infection on susceptibility of Asian citrus psyllid, Diaphorina citri, to selected insecticides

BACKGROUND: In the present investigation, the effect of Candidatus Liberibacter asiaticus (Las), a bacterium considered to be responsible for causing huanglongbing (HLB) disease in citrus, on the physiology of its vector, the Asian citrus psyllid (ACP) Diaphorina citri Kuwayama, was determined. Specifically, the effects of Las infection on the susceptibility of ACP to selected insecticides were determined. Furthermore, total protein content and general esterase activity were quantified in Las‐infected and uninfected ACP to gain insight into the possible mechanism(s) responsible for altered susceptibility to insecticides owing to Las infection. RESULTS: LC₅₀ values were significantly lower in Las‐infected than in uninfected ACP adults for chlorpyrifos and spinetoram. Furthermore, there was a general trend towards lower LC₅₀ values for three other insecticides for Las‐infected ACP; however, the differences were not statistically significant. Total protein content (µg mL^?1) was significantly lower in Las‐infected (23.5 ± 1.3 in head + thorax; 27.7 ± 1.9 in abdomen) than in uninfected (29.7 ± 2.1 in head + thorax; 35.0 ± 2.3 in abdomen) ACP. Likewise, general esterase enzyme activity (nmol min^?1 mg^?1 protein) was significantly lower in Las‐infected (111.6 ± 4.5 in head + thorax; 109.5 ± 3.7 in abdomen) than in uninfected (135.9 ± 7.5 in head + thorax; 206.1 ± 23.7 in abdomen) ACP. CONCLUSION: Susceptibility of ACP to selected insecticides from five major chemistries was greater in Las‐infected than in uninfected ACP. The lower total protein content and reduced general esterase activity in Las‐infected than in uninfected ACP may partly explain the observed higher insecticide susceptibility of Las‐infected ACP. Copyright © 2010 Society of Chemical Industry     

Influence of nitrogen fertilization and isoxaflutole on the nodulation of chickpea (Cicer arietinum)

The effects of soil nitrate and the herbicide, isoxaflutole, on chickpea nodulation were examined in a glasshouse experiment. The treatments consisted of one isoxaflutole‐tolerant and one isoxaflutole‐sensitive chickpea cultivar, five nitrate concentrations (0, 0.75, 1.5, 3.0, and 6.0 mmol L^?1), and three herbicide rates (0, 75 [the recommended rate], and 300 g ha^?1). The sensitive cultivar was more susceptible to isoxaflutole damage with an increasing herbicide rate and nitrate concentration, compared with the tolerant cultivar. Isoxaflutole at the recommended rate reduced the nodule dry weight of the sensitive cultivar by 51% and by 33% in the tolerant cultivar. The nodule dry weight of the sensitive cultivar was reduced by 28%, 40%, 64%, and 76% with the addition of the 0.75, 1.5, 3.0, and 6.0 mmol L^?1 nitrate concentrations, respectively. In comparison, the nodule dry weight of the tolerant cultivar was reduced by 50% and 79% at the 3.0 and 6.0 mmol L^?1 nitrate concentrations, respectively. In addition, the level of damage from increasing rates of isoxaflutole increased with the highest nitrate concentrations of 3.0 and 6.0 mmol L^?1, regardless of the cultivar. Isoxaflutole at the recommended application rate had a detrimental effect on the nodulation of both chickpea cultivars, but the isoxaflutole‐tolerant cultivar suffered less injury than the sensitive one in relation to some growth parameters. The damage to chickpea from the recommended rate of isoxaflutole also increased with soils of higher nitrate content.     

Design,synthesis and biological activities of new strobilurin derivatives containing substituted pyrazoles

BACKGROUND: Strobilurins are one of the most important classes of agricultural fungicides. To discover new strobilurin analogues with high activity, a series of new strobilurin derivatives containing substituted pyrazoles in the side chain were synthesised and bioassayed. RESULTS: The compounds were identified by ¹H NMR, IR, MS and elemental analysis. Preliminary bioassays indicated that some title compounds exhibited excellent fungicidal activities against Pseudoperonospora cubensis (Burk. & Curt.) Rostovsev and Erysiphe graminis DC f. sp. tritici Marchal, protecting cucumber and wheat at 6.25 and 1.56 mg L^?1 respectively, and showed a moderately high acaricidal activity against Tetranychus cinnabarinus (Boisd.) at 20 mg L^?1. The relationship between structure and biological activity is discussed in terms of effects of the substituent of the pyrazole ring. CONCLUSION: The present work demonstrates that strobilurin analogues with substituted phenylpyrazolylmethoxymethyl side chains can be used as possible lead compounds for further developing novel fungicides and acaricides. Copyright © 2009 Society of Chemical Industry     

Compounds from the subterranean part of Johnsongrass and their allelopathic potential

The allelopathic effects of the exotic invasive weed, Johnsongrass, on Lactuca sativa, a native plant in China, were evaluated and the phytotoxins were investigated under laboratory conditions. The crude extracts (chloroform and ethyl acetate fractions) that were obtained from the ethanol extract of the subterranean parts of Johnsongrass inhibited the germination speed and growth of the roots and shoots of the test plant. The four compounds, ethyl p‐hydroxybenzoate, diosmetin, apigenin, and luteolin, were isolated from the extract of the subterranean parts of Johnsongrass first, along with three other compounds (reported previously), p‐hydroxybenzaldehyde, p‐hydroxybenzoic acid, and dhurrin, and they all were evaluated on L. sativa. At the concentration of <0.5 mmol L^?1, ethyl p‐hydroxybenzoate, dhurrin, and the mixture of the compounds delayed the germination speed of the seeds of L. sativa at 24 h of incubation, while apigenin delayed the germination speed of the seeds of L. sativa at 72 h of incubation. Ethyl p‐hydroxybenzoate demonstrated the strongest delaying effect among the phenols and a similar effect was found with apigenin among the flavonoids, wheras ethyl p‐hydroxybenzoate induced a drastic inhibition of the germination at 2 mmol L^?1. In contrast, p‐hydroxybenzaldehyde and luteolin had no effect on the germination at any concentration at any stage. All the substances inhibited the shoot and root growth of L. sativa at 3 mmol L^?1. Increasing the concentration increased the inhibition of the growth of L. sativa. The inhibitory activity of ethyl p‐hydroxybenzoate and p‐hydroxybenzaldehyde was greater than that of the other compounds. This result suggested that the isolated phytotoxins might contribute to the successful invasion by Johnsongrass.     

Cytochrome P-450 in insects. 6. Age dependency and phenobarbital induction of cytochrome P-450, P-450 reductase,and monooxygenase activities in susceptible and resistant strains of Musca domestica

Development and phenobarbital (PB) induction of microsomal cytochrome P-450, cytochrome P-450 reductase, two epoxidation, and two O-demethylation activities were examined in chronologically timed populations of insecticide-susceptible (NAIDM) and -resistant (Rutgers) house flies. Measurements of these enzymes started with the pharate adult stage and ended 5 days following eclosion. Untreated insects of both strains had comparable reductase levels, whereas cytochrome P-450 and associated monooxygenase activities were 1.5-fold or more higher in Rutgers. Maximum induction, as well as toxicity, occurred at a lower PB concentration in NAIDM than Rutgers. The drug caused consistently higher increases in enzymes and activities within 12 hr of starting treatment in both strains. When PB was withdrawn from treated flies (both strains) 48 hr after treatment began, specific activities (product min^?1 mg protein^?1) in all enzymes returned to control values in 24 hr while metabolic capacity (product min^?1 insect^?1) achieved control values within 48 hr. The changes in turnover numbers (pmol product min^?1 pmol P-450^?1), in conjunction with the differences in the monooxygenation of the four substrates, suggest that PB treatment induced both a quantitative and qualitative change in NAIDM monooxygenation but only a quantitative change in Rutgers monooxygenation.