Balraj S. Parmar

Structure–biological activity relationships in triterpenic saponins: the relative activity of protobassic acid and its derivatives against plant pathogenic fungi

BACKGROUND Triterpenic saponins from Sapindus mukorossi Gaertn. and Diploknema butyracea JF Gmelin were evaluated for in vitro antifungal activity against four phytopathogenic fungi. The study of the structure-antifungal activity relationships of protobassic acid saponins was widened by including semi-synthetic derivatives. RESULTS Diploknema butyracea saponins exhibited significant antifungal activity against three fungi (ED(50) 230-455 microg mL(-1)), whereas S. mukorossi saponin was effective against two fungi (ED(50) 181-407 microg mL(-1)). The n-butanol extract after preparative HPLC separation provided two saponins from D. butyracea saponin mixture: 3-O-[beta-D-glucopyarnosyl-beta-D-glucopyranosyl]-16-alpha-hydroxyprotobassic acid-28-O-[arabinopyranosyl-glucopyranosyl-xylopyranosyl]-arabinopyranoside (MI-I), and 3-O-beta-D-glucopyranosyl-glucopyranosyl-glucopyranosyl-16-alpha-hydroxyprotobassic acid-28-O-[arabinopyranosyl-xylopyranosyl-arabinopyranosyl]-apiofuranoside (MI-III). The single saponin extracted from S. mukorossi saponin mixture was identified as 3-O-[O-acetyl-beta-D-xylopyranosyl-beta-D-arabinopyranosyl-beta-D-rhamnopyranosyl] hederagenin-28-O[beta-D-glucopyranosyl-beta-D-glucopyranosyl-beta-D-rhamnopyranosyl] ester (SM-I). Monodesmosides resulting from the partial degradation of hederagenin and hydroxyprotobassic acid bisdesmosides exhibited significant reduction in antifungal effect. Further removal of sugar moiety yielded complete loss in activity. The antifungal activity of the triterpenic saponins was associated with their aglycone moieties, and esterification of the hydroxyl group led to change in antifungal activity. CONCLUSION Sapindus mukorossi saponin, which is effective against Rhizoctonia bataticola (Taub.) Briton Jones and Sclerotium rolfsii Sacc., can be exploited for the development of a natural fungicide. A sugar moiety is a prerequisite for the antifungal activity of triterpenic saponin.

Screening for feeding deterrent and insect growth regulatory activity of triterpenic saponins from Diploknema butyracea and Sapindus mukorossi.

Antifeeding and insect growth regulatory effects of saponins and its hydrolyzed products from Diploknema butyracea and Sapindus mukorossi on the insect pest Spodoptera litura (F.) were investigated in the laboratory. D. butyracea saponins as well as their hydrolyzed prosapogenins were found to be better biologically active in controlling pests. A concentration of 1200 and 3400 mg L(-1) alkaline and acid hydrolyzed D. butyracea saponins exhibited significant antifeeding and toxic effects to third instar larvae when compared to the emulsified water as control. The n-BuOH extract after prep-HPLC separation provided two saponins from the D. butyracea saponin mixture: 3-O-[beta-D-glucopyarnosyl-beta-d-glucopyranosyl]-16-alpha-hydroxyprotobassic acid-28-O-[ara-glc-xyl]-ara (MI-I) and 3-O-beta-D-glucopyranosyl-glucopyranosyl-glucopyranosyl-16-alpha-hydroxyprotobassic acid-28-O-[ara-xyl-ara]-apiose (MI-III). The single saponin extracted from the S. mukorossi saponin mixture was 3-O-[beta-D-xyl(OAc).beta-D-arabinopyranosyl.beta-D-rhamnopyranosyl] hederagenin-28-O-[beta-D-glc.beta-D-glc.beta-D-rhamnopyranosyl] ester (SM-I). Five days after saponin treatment on larvae, the growth index (GI50) was reduced from 0.92% to 1520 ppm in alkaline hydrolyzed D. butyracea saponins. Upon hydrolysis, growth regulatory activity was improved in S. mukorossi saponin, whereas very little difference was found in antifeedant activity. Hydrophile-lipophile balance is important for the proper functioning of saponin/prosapogenin/sapogenin, which could be achieved by manipulating the sugar molecule in the triterpenic skeleton.

Effect of neem (Azadirachta indica A. Juss) seed kernel extracts on the larval parasitoid Bracon brevicornis Wesm. (Hym., Braconidae)

The alcoholic and hexane extracts of 17 neem ecotypes of India have been found to be toxic to the egg, larval and pupal stages of the cosmopolitan, external gregarious larval parasitoid Bracon brevicornis (Wesm.). In general, the hexane extracts showed higher toxicity against the egg and pupal stages whereas the alcoholic extracts were more toxic against the larvae. Azadirachtin content of the neem ecotypes revealed no apparent correlation with the observed toxicity against different stages of the parasitoid.

Controlled release formulations of acephate: Water and soil release kinetics

Controlled release formulations of insecticide acephate (O,S-dimethyl acetylphosphoramidothioate) have been prepared using commercially available polyvinyl chloride, carboxy methyl cellulose and carboxy methyl cellulose with kaolinite. Kinetics of acephate release in soil and water from the different formulations was studied in comparison with the commercially available formulation 75 DF. Release from the commercial formulation was faster than the new controlled pesticide release (CR) formulations. Addition of clay in the carboxy methyl cellulose matrix reduced the rate of release. The diffusion exponent (n value) of acephate in water and soil ranged from 0.462 to 0.875 and 0.420 to 0.547 respectively in the tested formulations. The release was diffusion controlled with a half release time (T1/2) of 2.97 to 52.41 days in water and 2.98 to 76.38 days in soil from different matrices. The maximum release of acephate in water and soil from controlled released formulations occurred between 6.33 to 36.34 and 12.49 to 29.09 days respectively. The results suggest that depending upon the polymer matrix used, the application rate of acephate can be optimized to achieve insect control at the desired level and period.

Field efficacy of azadirachtin‐A, tetrahydroazadirachtin‐A, NeemAzal® and endosulfan against key pests of okra (Abelmoschus esculentus)

UNLABELLED BACKGROUND Unlike synthetic pesticides, azadirachtin-based neem pesticides are environmentally friendly and are well known for their diverse pest control properties. Their use is, however, limited by the instability of azadirachtin, necessitating application at short intervals. The efficacy of relatively stable tetrahydroazadirachtin-A, therefore, needed to be established under field conditions. RESULTS Azadirachtin-A (Aza-A), its stable derivative tetrahydroazadirachtin-A (THA) and other neem pesticides have been evaluated for their field efficacy against major insect pests of okra, Abelmoschus esculentus (L.) Moench., during summer (kharif) 2003 and 2004. The optimum doses of Aza-A and THA against the fruit borer, Earias vittella F., were also established. Reductions in population of whitefly, Bemisia tabaci (Genn.), and leafhopper (jassid), Amrasca biguttulla biguttulla Ishida, after application of THA or endosulfan was evident up to 10 days after treatment (DAT), whereas with Aza-A and NeemAzal (NZ) the effect was observed up to 7 DAT only. Endosulfan and THA also caused higher reduction in the larvae of shoot and fruit borer E. vittella and E. insulana Boisd., and recorded the highest yields of 4600 and 4180 kg ha(-1). The efficacy of THA (0.05 g L(-1) emulsion) was comparable with that of 0.5 g L(-1) endosulfan emulsion in reducing fruit borer infestation, the reduction over the control being 86.0 and 87.3%, 84.9 and 94.1% and 90.2 and 92.6% at first, second and third picking. THA 0.02 g L(-1) and Aza-A 0.05 g L(-1) were on a par. Laboratory-made neem oil emulsifiable concentrate was the least effective, but was superior to untreated check. CONCLUSION Three consecutive sprays of THA, a neem-based biopesticide, and endosulfan have been found to be superior in controlling field pests of okra to Aza-A and NZ, which were on a par. THA thus holds potential as a component of pest management strategies against okra pests.

Pesticidal seed coats based on azadirachtin‐A: release kinetics, storage life and performance

BACKGROUND Infestation of seeds by pests during storage leads to deterioration in quality. Seed coating is an effective option to overcome the menace. Unlike synthetic fungicidal seed coats, little is known of those based on botanicals. This study aims at developing azadirachtin-A-based pesticidal seed coats to maintain seed quality during storage. RESULTS Polymer- and clay-based coats containing azadirachtin-A were prepared and evaluated for quality maintenance of soybean seed during storage. Gum acacia, gum tragacanth, rosin, ethyl cellulose, hydroxyethyl cellulose, polyethyl methacrylate, methyl cellulose, polyethylene glycol, polyvinyl chloride, polyvinyl acetate, polyvinyl pyrrolidone and Agrimer VA 6 polymers and the clay bentonite were used as carriers. The time for 50% release (t(1/2)) of azadirachtin-A into water from the seeds coated with the different coats ranged from 8.02 to 21.36 h. The half-life (T(1/2)) of azadirachtin-A in the coats on seed ranged from 4.37 to 11.22 months, as compared with 3.45 months in azadirachtin-A WP, showing an increase by a factor of nearly 1.3-3.3 over the latter. The coats apparently acted as a barrier to moisture to reduce azadirachtin-A degradation and prevented proliferation of storage fungi. Polyethyl methacrylate, polyvinyl acetate and polyvinyl pyrrolidone were significantly superior to the other polymers. Azadirachtin-A showed a significant positive correlation with seed germination and vigour, and negative correlation with moisture content. CONCLUSION Effective polymeric carriers for seed coats based on azadirachtin-A are reported. These checked seed deterioration during storage by acting as a barrier to moisture and reduced the degradation of azadirachtin-A.

Synthesis and Characterization of Poly (CMC-g-cl-PAam/Zeolite) Superabsorbent Composites for Controlled Delivery of Zinc Micronutrient: Swelling and Release Behavior

A series of novel superabsorbent hydrogel composites, poly(CMC-g-cl-PAam/Zeolite) (ZSAPC) were prepared by in situ graft polymerization using a cellulosic backbone, acrylamide and natural zeolite. The swelling and deswelling behavior of the prepared composites was evaluated and analyzed by different empirical models. The composite with optimum water absorption capacity were impregnated with ZnSO4 in situ during polymerization reaction. Zincated composites showed less water absorption capacity as compared to non-zincated ones. Zinc release behavior of zincated test hydrogel composites was studied in water and soil. All the test compositions exhibited non-Fickian or anomalous transport (0.43 < n < 0.84) and behaved as slow release products. GRAPHICAL ABSTRACT

Nitrification Inhibitors: Classes and Its Use in Nitrification Management

The explosive expansion of human activity during the last two centuries through industrial and agricultural pursuits has resulted in massive changes in the nitrogen (N) cycle of the planet. Based on the projected population growth and food demand, the N-fertilizer inputs into agricultural systems need to be doubled in the near future which would lead to further increase in the amount of N lost to the environment. If production agriculture continues to move towards high-nitrification agricultural systems with the expansion and intensification of agricultural activities, there is potential for catastrophic consequences to our planet due to the destruction of the ozone layer, global warming, and eutrophication. It is therefore imperative to manage the nitrification in agricultural systems for minimizing N leaks into the environment which are not only a serious economic and energy drain on society but also potentially have long-term ecological and environmental consequences. Currently, more than 60 % of the total N applied to agricultural systems is lost, amounting to an annual economic loss equivalent to US

Exploring the diversity of neem bioactives as eco-benign pesticides: a reappraisal

17 billion worldwide. Wide substrate range of ammonia monooxygenase (AMO), an important enzyme involved in nitrification, has enabled a range of chemicals or chemical formulations that can be effectively deployed as additives to N fertilizers to regulate nitrification. These chemicals by augmenting the efficiency of N-fertilizer use help us to achieve higher food production for catering the ever increasing population and minimize fertilizer-related pollution of the environment. This paper overviews N transformations in agricultural systems and the salient agrochemicals employed for management of nitrification, the most important transformation, in particular.

An efficient method for the purification and characterization of nematicidal azadirachtins A, B, and H, using MPLC and ESIMS

Biological activity of neem seeds, leaves and bark is well-established as feeding deterrent and growth disrupter against insects and other arthropods. Neem is a valuable natural pesticide with low toxicity for vertebrates. However, it has not yet achieved a prominent place among pesticides due to its unstability. Recent studies have focused on newer formulations like microencapsulation, inclusion complexes, microemulsion, and granular formulations to enhance efficacy shelf life. Several studies have been undertaken on the effects of neem on predator, parasitoids, and other beneficial organisms as well as impact on the environment. Biotechnological interventions have been carried out for mass production of the active molecule. Once stable formulations of the active molecules are developed, the farming community will benefit the most due to the low toxicity and marked efficacy of neem insecticides.