Effect of selectivity of herbicides and plant growth regulators used in sugarcane crops on immature stages of Trichogramma galloi (Hymenoptera: Trichogrammatidae)

Herbicides and plant growth regulators are often used in sugarcane management. However, the use of non-selective pesticides can cause adverse effects on the efficiency of beneficial insects in integrated pest management. Within this context, this study aimed to evaluate the effect of such products on the immature stages of the parasitoid Trichogramma galloi. Eggs of Diatraea saccharalis containing the parasitoid at the egg-larva stage and at the prepupal and pupal stages were immersed in test solutions of the following pesticides (maximum recommended doses for sugarcane): herbicides clomazone and diuron + hexazinone, and plant growth regulators trinexapac-ethyl and sulfometuron-methyl. The biological properties evaluated were emergence (F1 and F2) and number of eggs parasitized by T. galloi (F1). The products were classified according to percentage of reduction in emergence and parasitism: harmless (<30%), slightly harmful (30-79%), moderately harmful (80-99%) and harmful (>99%). The pesticides evaluated were considered to be harmless or slightly harmful to immature T. galloi and, thus, their use should be preferred for preserving this parasitoid species in sugarcane management programs.

Selectivity of chemical weed control systems in conventional cotton

Cotton is highly susceptible to the interference imposed by weed community, being therefore essential to adopt control measures ensuring the crop yield. Herbicides are the primary method of weed control in large-scale areas of production, and usually more than one herbicide application is necessary due to the extensive crop cycle. This study aimed to evaluate the selectivity of different chemical weed control systems for conventional cotton. The experiment took place in the field in a randomized block design, with twenty nine treatments and four replications in a split plot layout (adjacent double check). Results showed that triple mixtures in pre-emergence increased the chance of observing reductions in the cotton yield. To avoid reductions in crop yield, users should proceed to a maximum mixture of two herbicides in pre-emergence, followed by S-metolachlor over the top, followed by one post-emergence mixture application of pyrithiobac-sodium + trifloxysulfuron-sodium.

Trinexapac-Ethyl and Sulfometuron-Methyl Selectivity to Young Eucalyptus Plants

Trinexapac-ethyl and sulfometuron-methyl are the most widely used ripeners in sugarcane. The application is performed by airborne spraying. Thus, if weather conditions are unfavorable, spray drift to neighboring areas may occur. The objective of this study was to assess the selectivity of the plant growth regulators trinexapac-ethyl and sulfometuron-methyl, used as sugarcane ripeners, to eucalyptus (Eucalyptus urograndis) young plants. The experiment was installed in an eucalyptus commercial yield area, in the municipality of Tambaú, state of São Paulo, Brazil, and arranged in a 2 x 8 factorial design in randomized blocks with four replications. The treatments studied were trinexapac-ethyl and sulfometuron-methyl, sprayed in eight doses, 0; 1.0; 2.5; 5.0; 10; 25; 50 and 100% of the dose used in sugarcane as ripeners (200 g ha-1 of trinexapac-ethyl and 15 g ha-1 of sulfometuron-methyl). Chemical ripeners were applied on eucalyptus plants with 48 cm in height on average; 10.1 branches; 4.5 mm of stem diameter and 44.3 cm of crown diameter, at 46 days after seeding. Trinexapac-ethyl was selective to eucalyptus and stimulated crown diameter growth. At higher doses, sulfometuron-methyl promoted severe noticeable injuries in eucalyptus plants, such as apical bud death. However, during the assessment period the plants recovered and the visual symptoms of phytotoxicity and growth alterations were not observed at 60 days after application. The plant growth regulators trinexapac-ethyl and sulfometuron-methyl were selective to eucalyptus young plants.

Selectivity of Saflufenacil for Sweet Sorghum and Potential use of Na-Bentazon as a Safener

The objective of this study was to assess the selectivity herbicide saflufenacil for two sweet sorghum hybrids, when sprayed in preemergence and postemergence, besides the use of Na-bentazon as a 'safener' for saflufenacil. Three experiments were conducted, in pots, maintained in an ambient condition (second and third experiments) and in a greenhouse (first experiment). In each experiment a completely randomized distribution was used, with four replicates. In the first (2 x 6 factorial) two hybrids of sweet sorghum (CVSW 80007 and CVSW 80147) and six dosages (0; 35; 52.5; 70; 87.5 and 105 g ha-1) of saflufenacil were studied, applied in preemergence of the plants. In the second (2 x 5 factorial) the same hybrids of sweet sorghum sprayed in postemergence with saflufenacil (0; 35; 52.5; 70 and 87.5 g h-1) were assessed. In the third (4 x 5 factorial) the association of Na-bentazon (0; 240; 480 and 720 g ha-1) to saflufenacil (0.35; 52.5; 70 and 87.5 g ha-1) was studied, when sprayed in postemergence on the sweet sorghum plants (CVSW 80007). Hybrid CVSW 80147 was more tolerant to saflufenacil than hybrid CVSW 800007, in preemergence or postemergence applications. The variables that best assessed the sensibility of the sweet sorghum to saflufenacil were number of emerged plants, for preemergence applications, and dry matter of stem for postemergence. Na-bentazon showed promise for use as 'safener' in postemergence applications of saflufenacil in sweet sorghum for dosages up to 70 g ha-1.

SELECTIVITY OF FOMESAFEN TO COTTON

ABSTRACT The aim of this work was to evaluate the selectivity of fomesafen alone or in a tank mixture with other preemergent herbicides, with or without S-metolachlor application in early postemergence in cotton plant, cultivar DP 555 BG RR(r). The design utilized was a randomized complete block, organized in a split-plot arrangement, with four replications. For that, 24 herbicides were evaluated with fomesafen (0.45 and 0.625 kg ha-1), prometryn (1.25 kg ha-1), diuron (1.25 kg ha-1), trifluralin (1.8 kg ha-1), and S-metolachlor (0.77 kg ha-1), applied as preemergent, with or without S-metolachlor (0.77 kg ha-1) applied in early postemergence. The variables evaluated were: phytotoxicity, insertion height of the first reproductive branch, plant height, stand, number of reproductive branches per plant, number of bolls per plant, bolls weight, and productivity of cotton seed. Fomesafen alone or in a tank mixture with preemergent prometryn, diuron, trifluralin and S-metolachlor was selective to cotton plant. Preemergent fomesafen isolated application followed by the application of S-metolachlor in early postemergence was also selective. However, on average, preemergent tank mixtures applied in association with preemergent S-metolachlor early application was not selective to cotton crop.

SULFENTRAZONE SELECTIVITY AND EFFICIENCY IN CASSAVA CROPS IN SANDY AND CLAYEY SOILS

ABSTRACT Weeds have the potential to dramatically interfere in cassava cultivation, reducing its productive potential; however, there are few studies on the selective herbicides in this crop. Therefore, the objective was to evaluate in this work the selectivity and efficiency of sulfentrazone in cassava crops grown in sandy and clayey soils. Two experiments were carried out: The first one was carried out in sandy soil conditions in the conventional system; and the second one was carried out in clayey soil conditions in the no-tillage system. The experimental design was a randomized block with four replications. The treatments consisted in doses of 250, 500, 750 and 1,000 g ha-1 of sulfentrazone, and weeded and non-weeded controls. Sulfentrazone application in cassava crops has linearly reduced the production of roots in a proportion of 0.0153 and 0.0107 t ha-1 at each increment in grams of the active ingredient, respectively. It was concluded that sulfentrazone was not selective for cassava crops grown both in sandy and in clayey soil; however, it was highly effective in weed control in both soils.

Studies in selectivity of lipases in preparation of cyanohydrins, sugar conjugates and secondary alcohols

Biocatalysis can be applied in organic synthetic chemistry to counter challenges posed by increased demands towards chemo-, regio- and stereoselectivity, not forgetting the need for greener chemistry. During the last 30 years, biocatalysis with the use of enzymes as chiral catalysts has become more common in chemistry laboratories and industrial processes. In this thesis, the use of lipases as versatile biocatalysts in the acylation of alcohols is examined both in the light of literature examples and four original publications. In the first part of the work presented in this thesis lipases were utilized in two examples concerning secondary alcohols. First, the kinetic resolution of heterocyclic aromatic secondary alcohols through transesterification was thoroughly examined including the studies of competing hydrolysis and esterification reactions. In another example, lipases were utilized in the formation of a dynamic systemic resolution (DSR) process which in turn was used as a developmental tool in the optimization of the dynamic kinetic resolution (DKR) of five heterocyclic aromatic cyanohydrins in one pot for the preparation of cyanohydrin esters as single enantiomers. In the second part of the work, the regio- and stereoselectivity of lipases was used to form sugar conjugates of glyceric and β-amino acids. The primary hydroxyl groups of methyl α-D-galacto-, -gluco- and -mannopyranosides were now acylated trough lipasecatalyzed transesterification and enantioselective lipase-catalyzed ring-opening of β- lactams, respectively.

GABA-induced inactivation of Cebus apella V2 neurons: effects on orientation tuning and direction selectivity

We investigated the GABA-induced inactivation of V2 neurons and terminals on the receptive field properties of this area in an anesthetized and paralyzedCebus apella monkey. Extracellular single-unit activity was recorded using tungsten microelectrodes in a monkey before and after pressure-injection of a 0.25 or 0.5 M GABA solution. The visual stimulus consisted of a bar moving in 8 possible directions. In total, 24 V2 neurons were studied before and after blocker injections in 4 experimental sessions following GABA injection into area V2. A group of 10 neurons were studied over a short period. An additional 6 neurons were investigated over a long period after the GABA injection. A third group of 8 neurons were studied over a very long period. Overall, these 24 neurons displayed an early (1-20 min) significant general decrease in excitability with concomitant changes in orientation or direction selectivity. GABA inactivation in area V2 produced robust inhibition in 80% and a significant change in directional selectivity in 60% of the neurons examined. These GABA projections are capable of modulating not only levels of spontaneous and driven activity of V2 neurons but also receptive field properties such as direction selectivity.

Understanding the Origin of Selectivity in the Asymmetric Lithiation Reaction of N-Heterocycles: A Theoretical Study

The natural abundance of the N-heterocycle containing compounds has pushed the synthetic community toward the invention of new synthetic methods that result in the structural diversity of N-heterocycles. Among this, is the efficient and highly selective diamine mediated asymmetric lithiation process. Amongst the diamine chiral ligands, (-)-sparterine, which is a naturally occurring alkaloid proved to be an efficient one. Many successful, good yielding and highly selective lithiation reactions have been accomplished with the mediation by this chiral diamine base. Although, there are some examples of experimental and theoretical mechanistic studies in the literature, there is a lack of detailed understanding as to how it exactly induces the chirality. In this thesis is described a systematic investigation of how (-)-sparteine influences the stereoselectivity in the course of asymmetric lithiation reaction. This led us to the establishment of the function of A-ring’s β-CH2 effect and D-ring effect. Consequently, the importance of the A-ring and D-ring portions of (-)-sparteine in the stereoselectivity is unraveled. Another part of this thesis deals with the asymmetric lithiation of BF3-activated N,N- dimethylaminoferrocene in the presence of (1R, 2R)-N1,N2-bis(3,3-dimethylbutyl)-N1,N2-dimethylcyclohexane-1,2-diamine ( a (R,R)-TMCDA surrogate) with i-PrLi. Computational findings were in full accord with the experimental observations. Subsequently, the theoretically provided insights into the mechanism of the reaction were exploited in computational design of a new ligand. Unfortunately, the outcome of this design was not experimentally robust and an updated approach towards a successful design was explained.

Mirroring Enzymes: The Role of H-Bonding In HQuin-BAM Catalyzed Asymmetric Aza-Henry Reactions: A DFT Study into the Reactivity, Mechanism, and Origins of Selectivity

The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.

Use of cellular impedance to characterize ligand functional selectivity at G protein-coupled receptors

Les récepteurs couplés aux protéines G (RCPGs) représentent la plus grande famille de cibles thérapeutiques pour le traitement d’une panoplie de pathologies humaines. Bien que plusieurs décennies de recherche aient permis de façonner nos connaissances sur ces protéines membranaires, notre compréhension des déterminants moléculaires de leur activité signalétique reste encore limitée. De ces domaines de recherche, une avancée récente a mis à jour un nouveau phénomène, appelé sélectivité fonctionnelle des ligands, qui a bouleversé les paradigmes décrivant leu fonctionnement de ces récepteurs. Ce concept émane d’observations montrant que l’activité pharmacologique de certains ligands n’est pas nécessairement conservée sur tout le répertoire signalétiques connu du récepteur et peu se restreindre à l'activation sélective d’un sous-groupe de voies de signalisation.Ce nouveau modèle pharmacologique de l'activation des RCPG ouvre de nouvelles possibilités pour la découverte de médicaments plus efficace et sûr, ciblant les RCPGs. En effet, il permet la conception de molécules modulant spécifiquement les voies signalétiques d’intérêt thérapeutique, sans engager les autres voies qui pourraient mener à des effets secondaires indésirables ou de la tolérance. Cette thèse décrit l'utilisation d'une nouvelle approche sans marquage, basée sur la mesure du changement l'impédance cellulaire. Par la mesure des changements cellulaires, comme la morphologie, l’adhésion et/ou la redistribution des macromolécules, cette approche permet de mesurer de façon simultanée l'activité de plusieurs voies de signalisation impliqués dans ces réponses. Utilisant le récepteur β2-adrénergique (β2AR) comme modèle, nous avons démontré que les variations dans l’impédance cellulaire étaient directement liées à l’activation de multiples voies de signalisation suite à la stimulation du récepteur par son ligand. L’agoniste type du β2AR, l’isoprotérénol, s’est avéré induire une réponse d’impédance dose-dépendante constituée, dans le temps, de plusieurs caractéristiques distinctes pouvant être bloquées de façon compétitive par l’antagoniste ICI118,551 Par l’utilisation d’inhibiteurs sélectifs, nous avons été en mesure de déterminer la contribution de plusieurs voies signalétiques canoniques, comme les voies dépendantes de Gs et Gi, la production d’AMPc et l’activation de ERK1/2, sur ces changements. De plus, la dissection de la réponse d’impédance a permis d’identifier une nouvelle voie de mobilisation du Ca2+ contribuant à la réponse globale des changements initiés par la stimulation du β2AR. Dans une autre étude, nous avons rapporté que la réponse calcique induite par le β2AR serait attribuable à une transactivation Gs-dépendant du récepteur purinergique P2Y11, lui-même couplé à la protéine Gq. La mesure d’impédance permettant de distinguer et de décrire une pléiade d’activités signalétiques, nous avons émis l’hypothèse que des ligands arborant des profils signalétiques différents généreraient des réponses d’impédance distinctes. Le criblage d’une librairie de ligands spécifiques au β2AR a révélé une grande variété de signatures d’impédance. Grâce au développement d’une approche computationnelle innovatrice, nous avons été en mesure de regrouper ces signatures en cinq classes de composés, un regroupement qui s’est avéré hautement corrélé avec le profil signalétique des différents ligands. Nous avons ensuite combiné le criblage de composés par impédance avec l’utilisation d’inhibiteurs sélectifs de voies signalétiques afin d’augmenter la résolution du regroupement. En évaluant l’impact d’une voie signalétique donnée sur la signature d’impédance, nous avons été en mesure de révéler une plus grande variété de textures parmi les ligands. De plus, cette méthode s’est avérée efficace pour prédire le profil signalétique d’une librairie de composés non caractérisés, ciblant le β2AR. Ces travaux ont mené à l’élaboration d’une méthode permettant d’exprimer visuellement la sélectivité fonctionnelle de ligands et ont révélé de nouvelles classes de composés pour ce récepteur. Ces nouvelles classes de composés ont ensuite été testées sur des cardiomyocytes humains, confirmant que les composés regroupés dans différentes classes produisent des effets distincts sur la contractilité de ces cellules. Globalement, ces travaux démontrent la pertinence de l’utilisation de l’impédance cellulaire pour une évaluation précise des différences fonctionnelles parmi les composés ciblant les RCPGs. En fournissant une représentation pluridimensionnelle de la signalisation émanant des RCPGs à l’aide d’un seul essai ne requérant pas de marquage, les signatures d’impédance représentent une stratégie simple et innovante pour l’évaluation de la fonctionnalité sélective des ligands. Cette méthode pourrait être d’une grande utilité dans le processus de découverte de nouveaux médicaments.

Studies on the exploratory trawl fishing and significance of selectivity in trawl fishing gear for conservation of marine fishery resources with special reference to the inshore waters off Mangalore

School of Industrial Fisheries, Cochin University of Science and Technology

2(3H)-Furanones and related substrates: Synthetic strategies and selectivity profile in their reactivity

The synthesis and reactions of simple derivatives of 2(3H)- and 3(2H)furanones have attracted considerable attention in recent years, primarily in connection with development of routes to antitumor agents that contain this ring as central structural unit. They also serve as useful synthetic building blocks for lactones and furans and are the precursors of a wide variety of biologically important heterocyclic systems. Although a number of syntheses of furanones were known they were in many cases limited to specific substitution pattems. The development of altemative strategies for the preparation of these heterocycles is therefore of considerable importance or continues to be a challenge.We propose to develop new and general approaches to the synthesis of furanone ring systems from simple and readily available starting materials since we were interested in examining their rich photochemistry. The photochemical reactivity of Beta,gama-unsaturated lactams and lactones is a subject of current interest. Some of the prominent photoreaction pathways of unsaturated lactones include decarbonylation, solvent addition to double bonds, decarboxylation, migration of aryl substituents and dimerisation. lt was reported earlier that the critical requirement for clean photochemical cleavage of the acyl-oxygen bond is the presence ofa double bond adjacent to the ether oxygen and 2(3H)-furanones possessing this structural requirement undergo facile decarbonylation. But related phenanthrofuranones are isolated as photostable end products upon irradiation. Hence we propose to synthesis a few phenanthro-2(3H)-furanones to study the effect of a radical stabilising group at 3-position of furanone ring on photolysis. To explore the tripletmediated transformations of 2(3H)-furanones in polar and nonpolar solvents a few 3,3-bis(4-chlorophenyl)-5-aryl-3H-furan-2-ones and 3,3-di(p-tolyl)-5-aryl- 3H-furan-2-ones were synthesised from the corresponding dibenzoylstyrene precursors by neat thermolysis. Our aim was to study the nature of intermediates involved in these transformations.We also explored the possibility of developing a new and general approach to the synthesis of 3(2H)-furanones from simple and readily available starting materials since such general procedures are not available. The protocol developed by us employs readily available phenanthrenequinone and various 4-substituted acetophenones as starting materials and provides easy access to the required 3(2H)-furanone targets. These furanone derivatives have immense potential for further investigations .We also aimed the synthesis of a few dibenzoylalkene-type systems such as acenaphthenone-2—ylidene ketones and phenanthrenone-9-ylidene ketones. These systems were expected to undergo thermal rearrangement to give furanones and spirofuranones. Also these systems can be categorised as quinonemethides which are valuable synthetic intermediates.