Morphological characterization and distribution of antennal sensilla of Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae) using scanning electron microscopy.

Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae) is a serious polyphagous pest of various field and horticultural crops. A complete knowledge on the morphological features of antennal sensory structures is essential for efficient semiochemical-based control methods. The external structure and distribution of antennal sensilla in male and female adults of H. armigera were investigated using scanning electron microscopy. Eight distinct morphological types of sensilla were identified in both sexes: sensilla trichodea, sensilla basiconica, sensilla auricillica, sensilla coeloconica (multiporous), sensilla chaetica (uniporous), sensilla styloconica, sensilla squamiformia, and Böhm sensilla (aporous) in varying numbers and distribution along the length of the antennae. Of these sensilla, the most widespread are sensilla trichodea and sensilla basiconica on the antennae of both sexes. Female antennae have comparatively greater number of sensilla trichodea than male antennae. Among eight types of sensilla, sensilla basiconica, auricillica, styloconica type II, squamiformia, and Böhm sensilla were identified and reported for the first time in H. armigera. Sexual dimorphism in H. armigera was mainly detected as the variations in sensilla shape, numbers, and distribution of each type of sensilla. The sexual difference was observed in the numbers of sensilla coeloconica, chaetica, styloconica, and squamiformia per flagellomere. The possible functions of these sensilla were discussed in view of previously reported lepidopteran insects. The findings provide fundamental information on the morphology and distribution of antennal sensory structures in H. armigera. It would be useful for further detailed studies on physiological and behavioral function of each sensillum type and helpful for formulating related pest control methods.

Morphological characterization of antennal sensilla of Earias vittella (Fabricius) (Lepidoptera: Nolidae).

The shoot and fruit borer, Earias vittella Fab. (Lepidoptera: Nolidae) is an important and most devastating insect pest on okra and cotton. The pest mainly responsible for causing significant direct damage to tender shoots and fruits of okra, flowers and green bolls of cotton causing net yield loss in both crops. Many non-chemical control strategies have been developed under the insect pest management program, A complete knowledge on the antennal morphology of E. vitella is essential for future electrophysiological and behavioural studies. In the present study, the antennal morphology and types of sensilla on the antennae of both sexes of E. vitella were examined using light and scanning electron microscopy. Nine distinct types of sensilla were identified on the antennae of both sexes: sensilla trichodea, sensilla basiconica, sensilla coeloconica, sensilla auricillica (multiporous), sensilla chaetica, uniporous peg sensilla (uniporous), sensilla styloconica, sensilla squamiformia and bohm bristles (aporous). Among all sensilla, the most widespread are multiporous sensilla trichodea with 42.90 ± 1.77/flagellomere in male and 37.38 ± 1.38/flagellomere in female. Sensilla basiconica were the second most common sensillum type in male antennae with 15.67 ± 1.92/flagellomere. Other multiporous sensilla such as auricillica (11.90 ± 0.99) and coeloconica (4.57 ± 0.25) were significantly more abundant in female than in male antennae. Results of the study provide morphological evidence that E. vitella antennae possess microscopic cuticular structures that can play a role in perception of pheromones, plant odours and other chemical stimulants. This will open up opportunities to assess the possibility of using pheromones and plant-derived compounds for the monitoring or management of E. vittella moths in the agricultural landscapes.

Insect growth regulatory activity of carvacrol-based 1,3,4-thiadiazoles and 1,3,4-oxadiazoles.

In designing of novel insect growth regulators (IGRs), biologically occurring carvacrol has been structurally modified to thiadiazole and oxadiazole moieties. Two series of carvacrol analogs containing 1,3,4-thiadiazole (VIIIa-e) and 1,3,4-oxadiazole (IXa-e) derivatives are designed and synthesized. Their structures are confirmed by FT-IR, [Formula: see text] NMR, [Formula: see text]C NMR and LC-MS. IGR activity is tested against Spodoptera litura. Several analogs displayed IGR activity against this insect pest. Compounds VIIIe and IXe displayed relatively good IGR activity with [Formula: see text]values 117.43 and 108.83 ppm against Spodoptera litura, respectively. Synthesis, characterization and evaluation of carvacrol-based 1,3,4-thiadiazole and 1,3,4-oxadiazole derivatives as potent insect growth regulators (IGRs).

Effect of Nanohexaconazole on Nitrogen Fixing Blue Green Algae and Bacteria.

Nanohexaconazole is a highly efficient fungicide against Rhizoctonia solani. Nanoparticles are alleged to adversely affect the non-target organisms. In order to evaluate such concern, the present study was carried out to investigate the effect of nanohexaconazole and its commercial formulation on sensitive nitrogen fixing blue green algae (BGA) and bacteria. Various activities of algae and bacteria namely growth, N-fixation, N-assimilation, Indole acetic acid (IAA) production and phosphate solubilization were differently affected in the presence of hexaconazole. Although, there was stimulatory to slightly inhibitory effect on the growth measurable parameters of the organisms studied at the recommended dose of nanohexaconazole, but its higher dose was inhibitory to all these microorganisms. On the other hand, the recommended as well as higher dose of commercial hexaconazole showed much severe inhibition of growth and metabolic activity of these organisms as compared to the nano preparation. The uses of nanohexazconazole instead of hexaconazole as a fungicide will not only help to control various fungal pathogens but also sustain the growth and activity of these beneficial microorganisms for sustaining soil fertility and productivity.

Development and Quality Control of Nanohexaconazole as an Effective Fungicide and Its Biosafety Studies on Soil Nitifiers.

The study was aimed to develop a nano form of an existing fungicide for improving plant protection and reducing crop losses caused by fungal pathogens. The protocol for the preparation and estimation of nanohexaconazole was developed. Technically pure hexaconazole was converted into its nanoform using polyethyleneglycol-400 (PEG) as the surface stabilizing agent. Nanohexaconazole was characterized using Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS) studies. The average particle size of nanohexaconazole was about 100 nm. An analytical method was also developed for quality control of the nanofungicide by GLC fitted with flame ionization detector. Its limit of detection was 2.5 ppm. Fungicidal potential of nanohexaconazole was better in comparison to that of conventional hexaconazole. Hydrolytic and thermal stability studies confirmed its stability at par with the conventional formulation of fungicide. Impact of nanohexaconazole on soil nitrifiers was tested in vitro and there were no significant adverse effect in their numbers observed as compared to conventional registered formulation, proving the safety of the nanofungicide.

Bioefficacy evaluation and dissipation pattern of nanoformulation versus commercial formulation of pyridalyl in tomato (Solanum lycopersicum).

A study was undertaken to evaluate the decline of the residues of pyridalyl in tomatoes grown in two different cultivation systems: open field (conventional cultivation) and net house (pot experiment). Field experiment was conducted with commercial (10 EC) and nanoformulation of pyridalyl on tomato crop. Tomato plants were subjected to pesticide spray, when fruits were close to ripeness. Fruit samples were taken periodically and cleaned up using QuEChERS methodology, and the residue of pyridalyl was analyzed by ultrahigh-performance liquid chromatography (UHPLC). It dissipated in tomato fruit following the first-order kinetics. In field, average initial deposit of pyridalyl in tomato was observed to be 0.222 and 0.371 µg g(-1) at recommended and double the recommended application rate, respectively, using nanoformulation while it was 0.223 and 0.393 µg g(-1) on using commercial formulation, respectively. The half-life (t1/2) value of nanopyridalyl in tomato fruit was 2.8 and 3.2 days while for commercial formulation, it was 2.5 and 2.6 days for recommended and double the recommended dose, respectively. In India, maximum residue limit (MRL) on tomato has not been fixed for pyridalyl but its residues were always below European MRLs (5 µg g(-1)) on tomato at both application rates. The results of terminal residue showed that pyridalyl residues were below the available MRL. Low residues in tomatoes suggested that this pesticide is safe to use under the recommended dosage. No statistical differences were observed between the cultivation systems in relation to the residue levels of pyridalyl.

Insecticidal and antifeedant activities of clerodane diterpenoids isolated from the Indian bhant tree, Clerodendron infortunatum, against the cotton bollworm, Helicoverpa armigera.

The Indian bhant tree, Clerodendron infortunatum L. (Lamialus: Lamiaceae), is a well-known medicinal plant, but little information about its bioefficacy against agricultural pests exists. This scarcity was addressed in the present study, in which dried leaves of C. infortunatum were subjected to extraction with hexane and methanol and then partitioned using different solvents of varying polarity. In a preliminary bioassay, the antifeedant effects of the crude extracts and fractions were tested on a highly polyphagous pest, the cotton bollworm, Helicoverpa armigera Hübner (Lepidoptera: Noctuidae), using the no-choice test method with cabbage leaf discs. The methanol fraction resulted in maximum antifeedant activity. This fraction was further subjected to crystallization and column chromatography in order to isolate the compounds responsible for the activity. Three pure compounds were isolated and identified as clerodin (CL), 15-methoxy-14, 15-dihydroclerodin (MD), and 15-hydroxy-14, 15-dihyroclerodin (HD). The antifeedant activity of these compounds was studied using a choice as well as a no-choice test method with 24 and 48 hr observation periods. Insecticidal activity was measured using the topical application method at 0.5, 1, 1.5, 2, 2.5, and 3% concentrations, and data were recorded 24, 48, and 72 hr after treatment. In the no-choice test conditions, compounds CL and MD showed significantly higher antifeedant activity compared to the key ingredient in many commercial pesticides, azadirachtin, at its highest concentration. Compound HD also showed very good antifeedant activity, which did not differ significantly from that of azadirachtin. In the choice test conditions, all three compounds and azadirachtin showed 100% antifeedant activity at the highest concentration. Antifeedant Index (AI50) values of CL, MD, and HD were 6, 6, and 8 ppm in choice tests, and increased to 8, 9, and 11 ppm in the no-choice tests, respectively. Insecticidal activity of the isolated compounds was not significant compared to the control condition, even at the highest con-concentrations of the compounds. These results suggest that extracts of C. infortunatum have very good antifeedant effects against H. armigera due to the presence of specific compounds. These compounds could be utilized in the development of new biopesticides.

Sensitive and rapid determination of elemental nanosulfur/sulfur by liquid chromatography.

In order to identify the most suitable method for the estimation of nanosulfur for studying its residue dynamics, the present work was taken up. HPLC and GC methods were explored for its analysis. A comparative study of the existing analytical methods for the quality control of nanosulfur was undertaken. UV spectrophotometry and HPLC methods were superior with lower LOD when compared to GC-MS, which was not satisfactory due to breakage of catenated S20 into S6 and S8 . The method has been validated by analyzing various nanosulfur formulations of known concentrations. The recovery of the UV and HPLC methods ranged from 80.71 to 109.51% and 82.31 to 109.84%, respectively. The LOD of UV, GC-MS, and HPLC is 4, 20, and 1 ppm, respectively. The retention time of sulfur was 13.77 (HPLC), 2.89 (ultra high performance liquid chromatography), and 12.715 + 21.524 min (GC-MS). The method was successfully utilized for estimating sulfur in natural samples such as water from a sulfur hot spring and wastewater. The method has been validated by following the method recommended by the American Society for Testing and Materials. The HPLC method emerged as the best analytical method for the estimation of elemental sulfur.

Synthesis, biological activities and SAR studies of novel 1-Ethyl-7-methyl-4-oxo-1,4-dihydro-[1,8]naphthyridine-3-carboxylic acid based diacyl and sulfonyl acyl hydrazines.

BACKGROUND: Diacyl hydrazines have attracted significant interest in medicine, pesticide chemistry and material science. It is an important class of insect growth regulators. In this study, acyl hydrazine, the essential active group was incorporated in to nalidixic acid with the aim of combining the active groups to generate more potent agrochemical. RESULTS: Various nalidixic acid based diacyl and sulphonyl acyl hydrazines derivatives were synthesized and characterized by spectral techniques. These compounds were screened for the antifungal activity against five pathogenic fungi, nitrification inhibitory activity and insect growth regulator (IGR) activity against Spodoptera litura. The fungicidal activity was screened against R. bataticola, S. rolfsii, R. solani, F. oxysporum and A. porri. Most of the compounds showed moderate to good antifungal activity against A. porri (ED50 = 29.6-495.9 µg/mL). All the compounds showed significant nitrification inhibitory activity at 5% level. IGR activity was examined by feeding method against S. litura. CONCLUSION: The study revealed that a few compounds possessed good activity against three different pests namely certain fungus, soil bacteria and insect, among which, compound 37 (R' = 4-chlorophenyl) behaved the best.

Synthesis of novel 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-thiones and evaluation of their biocidal effects.

Novel 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-thiones have been synthesized in high yields by treatment of the corresponding oxo analogs with Lawesson's reagent. The structure has been confirmed by X-ray analysis. The compounds were tested for in vitro antifungal activity against Rhizoctonia bataticola, Sclerotium rolfsii, Fusarium oxysporum and Alternaria porii. The compounds exhibited moderate to good activity against all pathogens. Insecticidal activity of these compounds against Spodoptera litura was observed to be comparable to commercial pyrethroid insecticide, cypermethrin. The urease inhibitory activity has also been studied.

Bio-efficacy evaluation of nanoformulations of ß-cyfluthrin against Callosobruchus maculatus (Coleoptera: Bruchidae).

In the present investigation, bioefficacy of developed ß-cyfluthrin formulations, utilizing laboratory synthesized poly(ethylene glycols) based amphiphilic copolymers, were evaluated against Callosobruchus maculatus (Coleoptera: Bruchidae). The bioefficacy data indicated that the formulations developed by utilizing polymers having PEG - 1500 (3c) and PEG - 2000 (3d) as the hydrophilic segment showed greater efficacy after 14 days as evident from EC(50) values (2.2 and 1.58 mg L(-1) respectively). Also, release from the commercial SC formulation was faster than developed formulations as the commercial formulation had the lowest EC(50) value on the first day (0.51 mg L(-1)). The mean EC(50) of the commercial formulation against C. maculatus was quite high as compared to those of developed formulations. The results suggest that depending upon the polymer matrix used, the application rate of ß-cyfluthrin can be optimized to achieve insect control at the desired level and period. The results described in this paper are promising and provide a comparison of developed formulations with the commercial one showing an earlier degradation of ß-cyfluthrin in the latter and relatively prolonged activity in the former.

Synthesis and bioefficacy evaluation of new 3-substituted-3,4-dihydro-1,3-benzoxazines.

A new series of 1, 3-Benzoxazines were synthesized, characterized ((1)H NMR and (13)C NMR) and evaluated for their pesticidal activity. Six new 3-alkyl-3, 4-dihydro-4-methyl-2H-1, 3-benzoxazines (1-6) were prepared by hydroxymethylation of secondary amines with formaldehyde in 65-68% yields. These compounds were screened for there IGR activity against Spodoptera litura and for antifungal fungal activity in vitro against Sclerotium rolfsii ITCC 6181 by poisoned food technique. Insect Growth Regulatory (IGR) activity against Spodoptera litura showed that compound 3-Nonyl-3,4-dihydro-4-methyl-2H-1,3-benzoxazines was most effective as IGR with larval GI(50) of 1.863 mu g/Insect. Compounds 3-Octyl-3,4-dihydro-4-methyl-2H-1,3-benzoxazines and 3-Decyl-3,4-dihydro-4-methyl-2H-1,3-benzoxazines were effective IGRs. Antifungal screening revealed that compound 3-Dodecyl-3, 4-dihydro-4-methyl-2H-1,3-benzoxazines, was highly effective against Sclerotium rolfsii with LC(50) value 31.7 mg L(-1) comparable with commercial fungicide Hexaconazole (LC(50) 1.27 mg L(-1)). Also compounds 3-Nonyl-3, 4-dihydro-4-methyl-2H-1,3-benzoxazines and 3-Decyl-3,4-dihydro-4-methyl-2H-1,3-benzoxazines displayed promising fungitoxicity. The results described in this paper are promising and provides new array of synthetic chemicals to be utilized as pesticides.

An analysis of the persistence and potency of film-coated seed protectant as influenced by various storage parameters.

BACKGROUND: An efficient delivery system for seed-protectant chemicals is needed in light of several disadvantages of conventional seed treatment methods. This study evaluates the efficacy of film-coat application in maintaining the persistence and potency of imidacloprid on Lycopersicon esculentum (L.) Mill. seeds after simultaneous storage under ambient and regulated environment in paper and aluminium packages. RESULTS: High-performance liquid chromatography (HPLC) revealed 0.135 mg kg(-1) of herbage material to be the threshold value beyond which absolute control was obtained, and with film coating the latter was achieved even with half-dosage seed treatment, irrespective of the storage condition. The technique provided early protection to the crop and also nullified the deleterious effects of ambient storage on the persistence and potency of the pesticide. CONCLUSION: Film coating enabled superior pesticide dosage as well as higher biological efficacy to be achieved. Hence, in addition to being an ecofriendly alternative, the technique would be a more economically viable option for storage of treated seeds.

Synthesis and pesticidal activity of new N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines.

A series of novel N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines were synthesized as potential new agents to control pests. Their structures were confirmed on the basis of IR, NMR and elemental analyses. Six new N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines were prepared by reduction of corresponding Schiff bases using sodium borohydride in 80-87 % yields. These compounds were tested for their antifungal activity against two pathogenic fungi viz., Rhizoctonia bataticola ITCC 0482 and Sclerotium rolfsii ITCC 5226 and for insecticidal activity against insects of stored grain pest Callosobruchus analis. Fungicidal bioassay revealed that compound N-Decyl-N-[1-(2-hydroxyphenyl)ethyl]amine, was highly effective against R. bataticola (ED(50) 6.86 mg L(-1)) which was comparable with that of commercial fungicide hexaconazole (ED(50) 6.35 mg L(-1)). Also compounds N-Heptyl-N-[1-(2-hydroxyphenyl)ethyl]amine, N-Octyl-N-[1-(2-hydroxyphenyl)ethyl]amine and N-Nonyl-N-[1-(2-hydroxyphenyl)ethyl]amine displayed promising fungitoxicity against same pathogen. However, compound N-Heptyl-N-[1-(2-hydroxyphenyl)ethyl]amine was also found to be effective against S. rolfsii (ED(50) 4.92 mg L(-1) as against 1.27 mg L(-1) for hexaconazole). Compound N-Hexyl-N-[1-(2-hydroxyphenyl)ethyl]amine was most effective as insecticide followed by compound N-Octyl-N-[1-(2-hydroxyphenyl)ethyl]amine. LC(50) values for these compounds were 155.0 and 275.0 mg L(-1) respectively as against 36.70 mg L(-1) for commercial insecticide dichlorovos. The results obtained from bioassays indicate that this class of compounds can be utilized for the design of new substances endowed with pesticidal activities.