Synthesis and anticoccidial activities of novel ethyl 6-aryloxy-7-bromo-4-hydroxy-3-quinolinecarboxylate against Eimeria tenella

A series of novel 7-bromo substituted derivatives of quinolinecarboxylate (4a-i) have been synthesized with short synthetic route and high yields. The structures were confirmed by ¹H NMR, IR and MS. Anticoccidial activities of these compounds were evaluated according to the ACI (the anticoccidial index) method. The results indicated that four of the tested compounds (4a, 4b, 4e and 4g) exhibited anticoccidial activities obviously against Eimeria tenella at a dose of 27 mg kg⁻¹ in the chicken’ diet. In particular, the anticoccidial index of compound 4b (introduction 4-bromophenoxy at C-6 and bromine atom at C-7 of quinolinecarboxylate) was 170.0, which indicated that this compound has high anticoccidial activity.     

Synthesis, crystal structure, bioactivity and DFT calculation of new oxime ester derivatives containing cyclopropane moiety

A new series of oxime esters containing cyclopropane moiety were designed and synthesized. Their structures were confirmed by ¹H NMR, MS and elemental analysis. The single crystal structure of compound 7b was determined to further elucidate the structure. The KARI activity indicated that compound 7k exhibits favorable inhibition rate; the herbicidal assay showed that most of them have moderate activity against Echinochloafrumentacea, some of which have moderate activity against Brassica campestris.     

Comparative toxicity of several insecticides to eggs,larvae and adults of the Egyptian cottonworm,Spodoptera littoralis,in laboratory trials

Insecticides commonly used in cotton fields in Israel against lepidopterous pests were tested against eggs, as well as against 2nd-instar larvae and adults raised from eggs ofSpodoptera littoralis (Boisduval) collected in cotton fields in the Bet She’an Valley. Methomyl, chlorpyrifos, methidathion, monocrotophos, ethyl parathion, and methyl parathion were effective against eggs even at low doses, profenofos and phosfolan were less active, and azinphos-methyl was ineffective. The doses needed for 90% kill (LD ₉₀ ) of the 2nd-instar larvae were 8.5, 35, 280, 1300 and 3400 g a.i./1000 m ² for chlorpyrifos, methomyl, profenofos, methyl parathion and ethyl parathion, respectively; monocrotophos was inactive against 2nd-instar larvae even at relatively high doses. The LD ₉₀ of adults was reached with 16, 32, 1700 and 6100 ga.i./l000 m² of chlorpyrifos, methomyl, ethyl parathion and profenofos, respectively. Only chlorpyrifos and methomyl gave successful control of all three stages of the insect tested, at doses close to those generally used with aerial applications.     

Bacterial canker of cherry trees, <Emphasis Type="Italic">Prunus avium,</Emphasis> in South Africa

Laboratory and nursery experiments were conducted to identify the causal agent of a needle blight of Pinus wallichiana, a species native to the Western Himalayas. The pathogen was identified as Myrothecium verrucaria, on the basis of morphological, cultural and molecular characterization. BLAST analysis of ITS sequences of the pathogen revealed maximum sequence identity of 99% with M. verrucaria. The sequence is the first of this fungus from P. wallichiana. Phylogenetic analysis grouped all M. verrucaria isolates in a single clade; M. roridum and M. inundatum clustered in separate clades. The pathogen grew optimally at 25 ± 1 °C on oat meal agar, pH 5.5. Inoculation experiments with M. verrucaria demonstrated pathogenicity on Pinus halepensis, Cedrus deodara and Cryptomeria japonica, in addition to Pinus wallichiana.     

Insecticidal 3-benzamido-N-phenylbenzamides specifically bind with high affinity to a novel allosteric site in housefly GABA receptors

γ-Aminobutyric acid (GABA) receptors (GABARs) are an important target for existing insecticides such as fiproles. These insecticides act as noncompetitive antagonists (channel blockers) for insect GABARs by binding to a site within the intrinsic channel of the GABAR. Recently, a novel class of insecticides, 3-benzamido-N-phenylbenzamides (BPBs), was shown to inhibit GABARs by binding to a site distinct from the site for fiproles. We examined the binding site of BPBs in the adult housefly by means of radioligand-binding and electrophysiological experiments. 3-Benzamido-N-(2,6-dimethyl-4-perfluoroisopropylphenyl)-2-fluorobenzamide (BPB 1) (the N-demethyl BPB) was a partial, but potent, inhibitor of [³H]4′-ethynyl-4-n-propylbicycloorthobenzoate (GABA channel blocker) binding to housefly head membranes, whereas the 3-(N-methyl)benzamido congener (the N-methyl BPB) had low or little activity. A total of 15 BPB analogs were tested for their abilities to inhibit [³H]BPB 1 binding to the head membranes. The N-demethyl analogs, known to be highly effective insecticides, potently inhibited the [³H]BPB 1 binding, but the N-methyl analogs did not even though they, too, are considered highly effective. [³H]BPB 1 equally bound to the head membranes from wild-type and dieldrin-resistant (rdl mutant) houseflies. GABA allosterically inhibited [³H]BPB 1 binding. By contrast, channel blocker-type antagonists enhanced [³H]BPB 1 binding to housefly head membranes by increasing the affinity of BPB 1. Antiparasitic macrolides, such as ivermectin B_1a, were potent inhibitors of [³H]BPB 1 binding. BPB 1 inhibited GABA-induced currents in housefly GABARs expressed in Xenopus oocytes, whereas it failed to inhibit l-glutamate-induced currents in inhibitory l-glutamate receptors. Overall, these findings indicate that BPBs act at a novel allosteric site that is different from the site for channel blocker-type antagonists and that is probably overlapped with the site for macrolides in insect GABARs.     

Design, synthesis and antifungal/insecticidal evaluation of novel nicotinamide derivatives

A series of nicotinamide derivatives based on Boscalid were prepared and tested for their activities against seven plant pathogenic fungi and two insects. The preliminary bioassays indicated that almost all of the synthesized target compounds displayed the antifungal activities and some of them also had certain insecticidal activities. And, compound 12 showed the strongest activity of all against Rhizoctonia solani (EC₅₀ = 0.010 mg L⁻¹) and Sphaceloma ampelimum (EC₅₀ = 0.040 mg L⁻¹), even stronger than Boscalid, a new nicotinamide fungicide. Additionally, both compounds 1 and 2 showed strong activities against Plutella xylostella (90% and 80%, respectively, at 1000 mg L⁻¹).     

Insecticidal,repellent and fungicidal properties of novel trifluoromethylphenyl amides

Twenty trifluoromethylphenyl amides were synthesized and evaluated as fungicides and as mosquito toxicants and repellents. Against Aedes aegypti larvae, N-(2,6-dichloro-4-(trifluoromethyl)phenyl)-3,5-dinitrobenzamide (1e) was the most toxic compound (24 h LC₅₀ 1940 nM), while against adults N-(2,6-dichloro-4-(trifluoromethyl)phenyl)-2,2,2-trifluoroacetamide (1c) was most active (24 h LD₅₀ 19.182 nM, 0.5 μL/insect). However, the 24 h LC₅₀ and LD₅₀ values of fipronil against Ae. aegypti larvae and adults were significantly lower: 13.55 nM and 0.787 × 10⁻⁴ nM, respectively. Compound 1c was also active against Drosophila melanogaster adults with 24 h LC₅₀ values of 5.6 and 4.9 μg/cm² for the Oregon-R and 1675 strains, respectively. Fipronil had LC₅₀ values of 0.004 and 0.017 μg/cm² against the two strains of D. melanogaster, respectively. In repellency bioassays against female Ae. aegypti, 2,2,2-trifluoro-N-(2-(trifluoromethyl)phenyl)acetamide (4c) had the highest repellent potency with a minimum effective dosage (MED) of 0.039 μmol/cm² compared to DEET (MED of 0.091 μmol/cm²). Compound N-(2-(trifluoromethyl)phenyl)hexanamide (4a) had an MED of 0.091 μmol/cm² which was comparable to DEET. Compound 4c was the most potent fungicide against Phomopsis obscurans. Several trends were discerned between the structural configuration of these molecules and the effect of structural changes on toxicity and repellency. Para- or meta- trifluoromethylphenyl amides with an aromatic ring attached to the carbonyl carbon showed higher toxicity against Ae. aegypti larvae, than ortho- trifluoromethylphenyl amides. Ortho- trifluoromethylphenyl amides with trifluoromethyl or alkyl group attached to the carbonyl carbon produced higher repellent activity against female Ae. aegypti and Anopheles albimanus than meta- or para- trifluoromethylphenyl amides. The presence of 2,6-dichloro- substitution on the phenyl ring of the amide had an influence on larvicidal and repellent activity of para- trifluoromethylphenyl amides.     

First detection of Deformed wing virus of honeybees in Algeria

Deformed wing virus (DWV) is reported for the first time in honeybee colonies in Algeria.     

Natural diterpene β-lactone derivative as photosystem II inhibitor on spinach chloroplasts

α,7β-Dihydroxyvouacapan-17β-oic acid (1) was isolated from Pterodon polygalaeflorus Benth. Then, (1) was modified to obtain 6α-hydroxyvouacapan-7β,17β-lactone (2). Inhibition properties of both (1) and (2) were evaluated in spinach chloroplasts. Only compound (2) inhibited non-cyclic electron transport and ATP synthesis, i.e., (2) behaved as a Hill reaction inhibitor. Compound (2) did not affect photosystem I (PSI) activity but it did inhibit electron flow through PSII. Analysis of the partial PSII reactions from water to DCPIP_ox, water to silicomolybdate, and diphenylcarbazide to DCPIP_ox allowed locating inhibition sites at (i) the oxygen-evolving complex (OEC) and (ii) the redox enzymes of the electron transport chain, in the span of P₆₈₀ to Q_A. Chlorophyll a fluorescence measurements confirmed the action site for (2).     

Mosquito larvicidal activity of alkaloids from Zanthoxylum lemairei against the malaria vector Anopheles gambiae

Four alkaloids, 10-O-demethyl-17-O-methylisoarnottianamide 1, 6-acetonyl-N-methyl-dihydrodecarine 2, nitidine 3, and chelerythrine 4 were isolated from the plant Zanthoxylum lemairei (Rutaceae) and evaluated for mosquito larvicidal activity against the malaria vector Anopheles gambiae. The mortalities of the larvae were determined after 24 h. The results of the larvicidal tests demonstrated that compounds 1 and 2 were the most potent with mortality rates of 96.7% and 98.3% at a concentration of 250 mg/L, respectively. Compound 3 was less potent with a mortality of 28.3% at the same concentration. The percent mortality of 100% was observed at a concentration of 500 mg/L. The least potent of the four alkaloids was compound 4, which achieved 100% mortality at 1000 mg/L. These findings could be useful in the research for newer more selective, biodegradable and natural larvicidal compounds or can be used as lead compounds for the development of larvicides.     

Furanoditerpene ester and thiocarbonyldioxy derivatives inhibit photosynthesis

6α,7β-Dihydroxyvouacapan-17β-oic acid (1) and methyl 6α,7β-dihydroxyvouacapan-17β-oate (8) were isolated from Pterodon polygalaeflorus Benth. 1 was modified to obtain 6α-hydroxyvouacapan-7-β,17β lactone (2). Then, 6-oxovouacapan-7β,17β lactone (3) was obtained from 2. The furanoditerpene ester derivatives: propyl 7β-hydroxy-6-oxovouacapan-17β-oate (4), butyl 7β-hydroxy-6-oxovouacapan-17β-oate (5), 2-methoxyethyl 7β-hydroxy-6-oxovouacapan-17β-oate (6) and 3-methylbut-2-enyl 7β-hydroxy-6-oxovouacapan-17β-oate (7) were synthesized from (3) and methyl 6α,7β-thiocarbonyldioxyvouacapan-17β-oate (9) was obtained from (8). In this work, the lactone ester derivatives 4-7 and 9 were tested on photosynthetic activities in an attempt to search for new compounds as potential herbicide agents that affect photosynthesis. All compounds inhibited ATP synthesis and electron flow from water to MV, therefore, they act as Hill reaction inhibitors, being 4- to 9-fold more potent than 2 and 3 as inhibitors of ATP synthesis. Their interaction site was located at PSII in a similar way to diuron. Furthermore, furanoditerpene esters 6 and 7 act as uncouplers, and were corroborated by enhancement of the light-activated Mg²⁺-ATPase, while 5 act as an energy transfer inhibitor. Finally 5-7 behave as herbicides, since they inhibit the biomass production of weeds assay.     

Evaluation of insecticidal activity of podophyllotoxin derivatives against Brontispa longissima

Twenty podophyllotoxin analogues were first tested for their insecticidal activity against the fifth-instar larvae of Brontispa longissima in vivo. Among them, compounds 6-9 and 19 showed more promising and pronounced insecticidal activity than toosendanin, a commercial insecticide derived from Melia azedarach. The different insecticidal activity ranges of compounds 1-20 indicated that variation of chemical structures in the podophyllotoxin skeleton markedly affected the activity profiles of this compound class, and some important SAR information has been revealed from it. The results obtained from SAR analysis show good correlation with the docking models as well as with QSAR studies, which allows for the rational design of more potent podophyllotoxin derivatives in the development of potential new insecticides.     

Assessment of the antifungal activity of selected biocontrol agents and their secondary metabolites against <Emphasis Type="Italic">Fusarium graminearum</Emphasis>

Fusarium graminearum (teleomorph: Gibberella zeae) is the causal agent of several destructive diseases in cereal crops worldwide. In the present study we have evaluated the potential of two strains of Trichoderma sp. (T23, and T16), a strain of Paecilomyces sp. (PS1), and their secondary metabolites (SMs) in suppressing F. graminearum. Results from dual culture experiments show that in the presence of either Trichoderma sp., or Paecilomyces sp. mycelial growth of F. graminearum is considerably inhibited. Strain T23 causes the greatest inhibition (83.8%), followed by strain T16 (72.2%), and strain PS1 (61.9%). Likewise, mycelial growth of the pathogen is completely inhibited (≥ 98%) when grown under exposure to volatile metabolites excreted from Trichoderma cultures. Bioautographic analyses using culture filtrates revealed that several antifungal SMs are excreted. Among five metabolites tested, 6-pentyl-alpha-pyrone (6PAP) from strain T23, and PF3 from strain PS1 exhibit pronounced antifungal activity against F. graminearum. A new method for mass production of perithecia of F. graminearum which is simple and more effective than traditional methods was developed, which allows an increase in perithecial formation of more than 5-fold. Using this method, we found, that in the presence of SMs perithecial formation was negatively affected. Perithecial production was suppressed by 81.4% and 76.6% using 200 μg ml^?1 of either 6PAP or PF3, respectively. Moreover, ascospore discharge was significantly suppressed (67.0%) when perithecia were exposed to the metabolite F116 produced by T16. Including 6PAP or PF3 in conidial suspensions impeded germination of conidia completely. Similarly, both metabolites strongly inhibited ascospore germination (? 90%).     

Phenolic content as an indicator of tolerance of cowpea seedlings to <Emphasis Type="Italic">Sclerotium rolfsii</Emphasis>

The role of phenolics in plant tolerance to pathogen infection is well documented. The objective of the present preliminary investigation was to study phenolic metabolites involved in the tolerance or susceptibility of cowpea (Vigna unguiculata Walp.) cultivars to Sclerotium rolfsii Sacc. and to use their presence as a possible screening tool. Total, free acid, ester-bound and cell wall-bound phenolics of 10 cowpea cultivars were quantified. In healthy seedlings, the tolerant cultivars displayed the higher phenol content than the susceptible cultivars. In S. rolfsii infected seedlings, the highest increase was found from 48 h after inoculation. The net effect of inoculation was a 630% increase in total phenolics (soluble and insoluble) in the stem of tolerant cultivars while the total phenolic content increased only by 212% in the stems of susceptible cultivars. Although, no significant difference (P = 0.05) was detected among cultivars, in terms of free acid phenolics, the amount of ester-bound and cell wall-bound phenolics significantly increased, therefore demonstrating a similar trend to the one observed for the total phenolic content. These preliminary results showed that the presence of phenolics before and after S. rolfsii infection may be used as a rapid screening method for detection of tolerance to S. rolfsii damping-off and stem rot of cowpea.     

Insecticidal activity and mode of action of novel nicotinoids synthesized by new acylpyridinium salt chemistry and directed lithiation

Novel acylpyridinium salt chemistry and directed lithiation methodology was developed to add for the first time substitutions directly to the phenylpyridine heterocyclic ring of nicotine. A variety of 3-(1-methylpyrrolidin-2-yl)-4-(alkyl, aromatic, heterocyclic and silanyl) and -N-alkyl pyridines were synthesized (compounds 1-9). In vial tests with the green peach aphid, Myzus persicae, compounds 1-4 were 1.1, 1.8, 2.3 and 1.9×, respectively, more active than nicotine and 64, 40, 31 and 38×, respectively, less active than acetamiprid. Against the western flower thrips, Frankliniella occidentalis, 1-4 were 1.4, 2.1, 2.0 and 1.6×, respectively, more active than nicotine and 9, 6, 6 and 8×, respectively, less active than acetamiprid. For the cotton aphid, Aphis gossypii, the activity of 1-9 was similar to nicotine. Compounds 7 and 9 when incorporated into artificial diet produced low mortality for larvae of the beet armyworm, Spodoptera exigua, but were not active against the corn earworm, Helicoverpa zea. When 1-4 and 6-9 were injected into larvae of the beet armyworm, a variety of symptoms similar to acetamiprid were observed which included tremors, uncoordinated movement, diuresis, paralysis and death. In addition, imidacloprid-binding to membranes from the house fly head, Musca domestica, was inhibited by compounds 1-9, when using a concentration range of 1-100 μM. These studies demonstrate that our new chemistry enhances the insecticidal activity of nicotine with an apparent mode of action as an acetylcholine agonist.     

Biocontrol of <Emphasis Type="Italic">Fusarium</Emphasis> wilt of <Emphasis Type="Italic">Capsicum annuum</Emphasis> by rhizospheric bacteria isolated from turmeric endowed with plant growth promotion and disease suppression potential

In the present study, 129 rhizospheric bacteria isolated from Curcuma longa were screened for their antagonistic potential against six fungal phytopathogens. Among them, 32 isolates that showed significant antagonistic potential were screened for their in vitro plant growth promoting (PGP) traits. The identification of potential isolates was confirmed by 16S rRNA gene sequencing and results revealed Bacillus as the dominant genus followed by Staphylococcus, Pseudomonas, Sphingomonas and Achromobacter. Based on the antagonistic activity and PGP traits; two strains (BPSRB4 and BPSRB14), identified as Bacillus amyloliquefaciens, were further tested for their in vivo PGP and disease suppression potential on Capsicum annuum seedlings under greenhouse conditions. The results demonstrated that BPSRB4 and BPSR14 strains suppress fungal pathogen infection and promote plant growth. Further, the BPSRB4 strain was positive for the production of the phytohormone indole acetic acid (IAA) detected by thin layer chromatography (TLC). In addition, nitrogen fixation and plant growth promotion activity were also confirmed by amplification and sequencing of nitrogen fixation gene (nifH) and ACC (1-aminocyclopropane-1-carboxylate) deaminase (acdS) gene from strains BPSRB4 and BPSRB14. The present study demonstrated that the B. amyloliquefaciens strains BPSRB4 and BPSR14 possess antagonistic activity and PGP potential which could be explored for the development of biofertilizers and biocontrol agents for the growth of chilli seedlings.     

A new species of <Emphasis Type="Italic">Anagyrus</Emphasis> (Hymenoptera: Encyrtidae) from China,parasitoid of <Emphasis Type="Italic">Phenacoccus solani</Emphasis> Ferris (Hemiptera: Pseudococcidae) on <Emphasis Type="Italic">Lycoris radiata</Emphasis> (L’Her.) Herb.

A new species of Anagyrus Howard (Hymenoptera: Encyrtidae), A. pseudofuscus Zu sp. nov., is described from China as a parasitoid of the mealybug, Phenacoccus solani Ferris (Hemiptera: Pseudococcidae).     

Influence of exogenous cholesterol in Pythiaceae resistance to inhibition by <Emphasis Type="Italic">Trichoderma</Emphasis> antibiosis

The purpose of this study was to determine if exogenous cholesterol availability influenced Pythiaceae resistance to antibiosis. Characterisation of an isolate of Phytophthora erythroseptica and Pythium ultimum for tolerance to antibacterial compounds found that 0.05 g.l^?1 chloramphenicol inhibited mycelial growth by 96.6 % and 23.5 % respectively. However, the addition of cholesterol (0.01 g l^?1) to potato dextrose agar (PDA) containing 0.05 g l^?1 chloramphenicol was found to increase mycelial growth of P. erythroseptica, indicating a role for cholesterol in tolerance to inhibitory antibacterial compounds. To determine if this property extended to suppressive effects of a potential biocontrol agent, P. erythroseptica and P. ultimum were then tested against a cell-free filtrate of diffusible metabolites produced by a suppressive Trichoderma harzianum isolate in the presence and absence of cholesterol in PDA. In the absence of cholesterol, diffusible metabolites of the T. harzianum isolate were found to inhibit mycelial growth of P. erythroseptica and P. ultimum on PDA by 98 % and 63.6 % respectively (P?<?0.0001). However, the inhibitory effect of the metabolites was mitigated when 0.005 g l^?1 of cholesterol was present in PDA, with mycelial growth of P. ultimum and P. erythroseptica reduced by only 60.4 % and 41.8 %, respectively (P?<?0.0001), much less inhibition than was observed in the absence of cholesterol. These results demonstrated that access to exogenous cholesterol can influence the sensitivity of Pythiaceae species to antibiosis by positively influencing mycelial growth.     

Are field populations of arbuscular mycorrhizal fungi able to suppress the transmission of seed-borne <Emphasis Type="Italic">Bipolaris sorokiniana</Emphasis> to aerial plant parts?

The development of seed-borne Bipolaris sorokiniana in barley in the presence of arbuscular mycorrhizal fungi was studied. To exploit natural variation in their ability to control disease development, arbuscular mycorrhizal fungi from various Swedish arable soils were multiplied in trap cultures using a mixture of plant species. Six out of eight trap culture soil inocula were able to reduce transmission of B. sorokiniana from seeds to stem bases when grown together with infected barley seed. Based on this result two soil inocula, of different origin, from semi-natural grassland and barley respectively, were chosen for further greenhouse studies. Both soil inocula gave significant reductions in pathogen transmission from seeds to seedlings compared to the untreated control. In addition, treatment with spore inocula, collected from the different trap culture soils, showed disease suppression. Treatment with spores from the pure culture Glomus intraradices gave significant reduction in leaf lesion development. A treatment with the commercial inoculum Vaminoc^® was included and gave some suppression of the pathogen. In conclusion this study has shown that AM soil inocula from trap cultures suppressed the transmission of seed-borne B. sorokiniana in the aerial parts of barley plants.     

Pathogenicity and Fungicide Sensitivity of <Emphasis Type="Italic">Rhizoctonia solani</Emphasis> and <Emphasis Type="Italic">R. cerealis</Emphasis> Isolates

The Rhizoctonia solani species consists of multinucleate isolates that belong to anastomosis groups AG1–AG3 and differ in virulence and host affinity. R. cerealis is a binucleate species of anastomosis group AG-D which causes sharp eyespot, a common plant disease in Poland. Rhizoctonia spp. is a ubiquitous soil pathogen that poses a significant threat for global crop production due to the absence of effective crop protection products. The aim of this study was to determine the virulence of R. solani and R. cerealis isolates towards Beta vulgaris, Zea mays, Triticum spelta and T. aestivum seedlings, to confirm the presence of endopolygalacturonase genes pg1 and pg5 in the genomes of the tested isolates and to evaluate the tested isolates’ sensitivity to triazole, strobilurin, imidazole and carboxamide fungicides. All tested isolates infected B. vulgaris seedlings. but none of them were virulent against Z. mays plants. R. solani isolates AG4 PL and AG2-2IIIB PL were characterized by the highest virulence (average infestation score of 2.37 and 2.53 points on a scale of 0–3 points) against sugar beet seedlings. The prevalence of infections caused by most of the analysed isolates (in particular R. solani AG4 J—11.8, and R. cerealis RC2—0.78) was higher in spelt than in bread wheat. The virulence of the analysed isolates was not correlated with the presence of pg1 and pg5 genes. The efficacy of the tested fungicides in controlling Rhizoctonia spp. infections was estimated at 100% (propiconazole + cyproconazole), 98.8% (penthiopyrad), 95.4% (tebuconazole) and 78.3% (azoxystrobin).