Doctor of Philosophy / Department of Biochemistry / John M. Tomich / Channel replacement therapy represents a new treatment modality that could augment existing therapies against cystic fibrosis. It is based on designing synthetic channel-forming peptides (CFPs) with desirable selectivity, high ion transport rates and overall ability to supersede defective endogenous chloride channels. We derived synthetic CFPs from a peptide initially reconstituted from the second transmembrane segment of the α-subunit of Glycine receptor (M2GlyR). Our best candidate peptide NK4-M2GlyR T19R, S22W (p22-T19R, S22W) is soluble in aqueous solutions, has the ability to deliver itself to the epithelial cell membranes without the use of a delivery system, is non-immunogenic, but when assembled into a pore, lacks the structural properties for anion selectivity. Previous findings suggested that threonine residues at positions 13, 17 and 20 line the pore of assembled p22-T19R, S22W and recent studies indicated that an introduction of positively charged 2, 3-diaminopropionic acid (Dap) at either T13 or T17 in the sequence increases transepithelial ion transport rates across the apical membranes of Madin-Darby canine kidney (MDCK) epithelial cells. This study focused on further structural modifications of the pore-lining interface of p22-T19R, S22W assembled pore. It was hypothesized that singly, doubly or triply introduced Dap residues modify the pore geometry and that their positively charged side chains impact discrimination for anions. Dap-substituted p22-T19R, S22W peptides retain the α-helical secondary structure characteristic for their parent p22-T19R, S22W. The sequences containing multiple Dap-substituted residues induce higher short circuit current across the epithelial MDCK cells compared to peptides with single Dap-substitutions or no Dap-substitutions. Whole-cell voltage clamp recordings using Xenopus oocytes indicate that Dap-substituted peptide assemblies induce higher levels of voltage-dependent but non-selective ion current relative to p22-T19R, S22W. Studies using the D-enantiomer of p22-T19R, S22W and shorter truncated sequences of a full length L-p22-T19R, S22W and L-Dap-substituted peptides provided evidence that peptide-induced ion transport rates can be attributed to formation of de novo pathways. Results of preliminary computer modeling studies indicate that Dap residues affect the pore geometry but not ion selectivity. Future studies focusing on modifying the existing electrostatic environment towards anion selectivity will focus on staggering the charged residues of Dap at various locations inside synthetic pores.

Orientador: Dagoberto Martins / Banca: Carlos Gilberto Raetano / Banca: Mario Sergio Tomazela / Resumo: Este trabalho teve como objetivo avaliar a seletividade do herbicida saflufenacil de forma isolado e em mistura, aplicado em pós-emergência inicial sobre 10 variedades de cana-de-açúcar em condição de cana-soca. O experimento foi instalado no município de Botucatu/SP. O delineamento experimental utilizado foi o de blocos casualizados em parcelas subdivididas com quatro repetições, sendo as variedades dispostas nas parcelas e os herbicidas nas subparcelas. Os tratamentos utilizados foram: saflufenacil + Assist (0,07 kg ha-1 + 0,5% v/v); saflufenacil + Break Thru (0,140 kg ha-1 + 0,05% v/v); saflufenacil (0,280 kg ha-1) e ametryne + clomazone (3,0 + 2,0 L i. a. ha-1), aplicados aos 49 DAC (dias após o corte), além de uma testemunha sem aplicação. As plantas encontravam-se por ocasião da aplicação com 2 a 4 folhas. As dez variedades utilizadas foram: SP83-2847, SP80-3280, RB855453, SP80-1842, SP89-1115, RB867515, PO8862, RB855156, SP80-1816 e SP81-3250. Para a aplicação das caldas herbicidas utilizou-se um pulverizador costal pressurizado a CO2 equipado com barra de aplicação com seis pontas Teejet XR 110 02 VS, à 200 kPa no volume de aplicação de 200 L ha-1. As avaliações visuais de controle foram realizadas aos 3, 7, 15, 21, 30, 45 e 60 dias após a aplicação. As injúrias visuais observadas nas plantas de cana-de-açúcar foram dependentes da variedade analisada e dos herbicidas e doses em teste. Todos os tratamentos químicos foram seletivos as diferentes variedades estudadas, não afetando o rendimento de colmos / Abstract: This study aims to evaluate the selectivity of the herbicide saflufenacil applied alone and mixed, in post-emergence over ten sugarcane varieties in the second year after planting. The experiment was carried out in Botucatu/SP. The experimental design was a randomized split plot with for replications, and the varieties in the plot and subplot herbicides. The treatments were: saflufenacil + Assist (0.07 kg ha-1 + 0,5 v/v); saflufenacil + Break Thru (0.140 kg ha-1 + 0.05% v/v); saflufenacil (0.280 kg ha-1) and ametryne + clomazone (2.0 + 3.0 L ha-1) applied to the 49 DAH (days after first harvest), and a control without application. The plants were at 2 to 4 leaves in the application time. The varieties were: SP83-2847, SP80- 3280, RB855453, SP80-1842, SP89-1115, RB867515, PO-8862, RB855156, SP80-1816 and SP81-3250. For herbicide application was used the Teejet XR 11002 VS spray equipment with six spray nozzles type, at 200 kPa and, 200 L ha-1 spray volume. The visual injuries observed in plants of sugarcane were dependent of varieties and the herbicides and, doses tested. All chemical treatments tested were selective to different varieties studied, without affecting the crop production / Mestre

La performance des procédés de séparation des xylènes utilisant des adsorbants nanoporeux est liée aux propriétés de transport et de sélectivité des zéolithes faujasite du type BaX. Les zéolithes conventionnelles présentent un grand volume de micropores et une bonne sélectivité vis-à-vis du paraxylène. Cependant, la diffusion intracristalline est un processus lent qui limite l'efficacité des zéolithes. Par conséquent, l'utilisation de zéolithes hiérarchiques a été proposée comme alternative pour améliorer les propriétés de transport par l'introduction d'un réseau poreux supplémentaire. Dans cette thèse, deux types de zéolithes hiérarchiques BaX sont considérés: les agrégats de nanoparticules (NA - des agrégats de petites particules avec des mésopores entre eux) et les zéolithes Layer-Like (LL), formées par un réseau de couches zéolitiques (présentant des mésopores entre les couches et au sein des couches). Afin de mieux comprendre le rôle joué par la surface externe et par la porosité supplémentaire dans les zéolithes hiérarchiques (NA et LL), ces zéolithes ont été caractérisées en termes de quantité et de qualité de la surface externe par différentes techniques de caractérisation (diffraction des rayons X, adsorption de N2, porosimétrie, microscopie, infrarouge et résonance magnétique nucléaire). L'adsorption et la diffusion des xylènes ont été évaluées par thermogravimétrie et par batch, en phase gazeuse et liquide, respectivement. Les expériences réalisées en phase liquide permettent d’observer une amélioration importante de la diffusion des xylènes dans les zéolithes hiérarchiques. Néanmoins, une perte significative de la para-sélectivité dans les zéolites BaX hiérarchiques est observée par rapport aux zéolites BaX conventionnelles. L'étude de la diffusion en phase gazeuse a permis d'identifier des barrières de surface, qui sont absentes en phase liquide. Cela peut indiquer qu’à forte concentration , le passage des molécules à travers la surface est moins perturbé. Ceci renforce l'intérêt d’utiliser les zéolithes hiérarchiques pour la séparation des xylènes qui est opérée en phase liquide / The performance of xylene separation processes using nanoporous adsorbents is related to both the transport and selectivity properties of the used faujasite zeolites (BaX). Conventional zeolites exhibit a large volume of micropores and a good selectivity to paraxylene (px). However, intracrystalline diffusion is a slow process which limits the efficiency of the zeolites. Therefore, the use of hierarchical zeolites has been proposed as an alternative to improve transport properties by the introduction of an additional porous network. In this thesis, two types of BaX hierarchical zeolites are considered: Nanoparticles aggregates (NA - aggregates of small particles with mesopores between them) and Layer-like zeolite (LL - array of zeolite layers, with the presence of inter and intra-layers mesopores). In order to better understand the role played by the external surface and by the additional porosity in hierarchical zeolites (NA and LL), these zeolites were characterized in terms of quantity and quality of the external surface by the application of different characterization techniques (X-ray diffraction, N2 adsorption, porosimetry, microscopy, infrared and nuclear magnetic resonance). The xylene adsorption and diffusion were evaluated in gas and liquid phase, by means of thermogravimetry and batch experiments, respectively. Through the experiments in liquid phase, it is noticed that the xylene diffusion in hierarchical zeolites is considerably improved. On the other hand, a significant loss in px-selectivity in hierarchical BaX zeolites is observed compared to conventional BaX zeolites. The study of diffusion in gas phase allowed the identification of surface barriers, which are not present in the liquid phase. This may be an indication that, when the concentration around the surface is large (liquid phase), the passage of molecules across the surface is less/not disturbed. This reinforces the interest of using hierarchical zeolite for xylene separation which is carried out in liquid phase

O parasitoide Ageniaspis citricola Logvinovskaya é o principal agente de controle biológico do minador-dos-citros Phyllocnistis citrella Stainton. No entanto, com a detecção do huanglongbing houve um aumento no uso de inseticidas nos pomares cítricos e não se conhece seus efeitos à A. citricola. Desta maneira, estudou-se o efeito letal de cinco inseticidas e a persistência aos 3, 7, 10, 17 e 24 dias após a pulverização em mudas de citros mantidas em casa de vegetação ao parasitoide A. citricola, nas dosagens especificadas (g i.a. L-1): imidacloprido 0,04 (Provado&reg; 200 SC), clorpirifós 0,72 (Lorsban&reg; 480 BR), bifentrina 0,02 (Talstar&reg; 100 EC), beta-ciflutrina 0,0125 (Turbo&reg; 50 EC), abamectina 0,0054 (Vertimec&reg;), bem como o efeito subletal no parasitismo em fêmeas expostas por 24 horas aos resíduos de abamectina. Imidacloprido, clorpirifós, bifentrina e beta-ciflutina foram considerados nocivos para adultos de A. citricola (M > 75%), enquanto que, abamectina foi considerado inócuo (M < 25%). Com base na duração do efeito nocivo, clorpirifós e beta-ciflutrina foram considerados de vida curta (< 5 dias), enquanto que, imidacloprido foi levemente persistente (5-15 dias) e bifentrina moderadamente persistente (16-30 dias). Abamectina não alterou a taxa de parasitismo de A. citricola, mas alterou substancialmente a razão sexual (0,11) quando comparado ao tratamento controle (0,5). Os resultados indicam que deve-se ter cautela em recomendar os produtos avaliados, observando-se o efeito residual daqueles produtos considerados nocivos à A. citricola, de forma a explorar a seletividade ecológica. Abamectina, embora inócua a adultos do parasitoide, pode levar a uma redução populacional de A. citricola, devendo-se realizar estudos de campo para elucidar essa questão. / Ageniaspis citricola Logvinovskaya is the main biological control agent of Phyllocnistis citrella Stainton. However, with the huanglongbing report, there was an increase in the use of insecticides in citrus orchards and the effects on A. citricola are not known. Thus, we studied the lethal effects of five insecticides and the persistence on 1, 3, 7, 10, 17 and 24 days post application in seedlings of citrus kept in greenhouse, using the specified dosages (g a.i. L-1): imidacloprid 0.04 (Provado&reg; 200 SC), chlorpyriphos 0.72 (Lorsban&reg; 48 BR), bifenthrin 0.02 (Talstar&reg; 10 EC), beta-cyfluthrin 0.0125 (Turbo&reg; 5 EC), abamectin 0.0054 (Vertimec&reg; 18 EC), as well as the sublethal effect on the parasitism by females exposed to residues of 24 hours of abamectin. Imidacloprid, chlorpyriphos, bifenthrin and beta-cyfluthrin were considered harmful to A. citricola (M > 75%) and abamectin were considered harmless (M < 25%). Chlorpyriphos and beta-cyfluthrin were considered of short life (< 5 days), imidacloprid slightly persistent (5-15 days) and bifenthrin moderately persistent (16-30 days). Abamectin did not affect the parasitism by A. citricola, but the sex ratio, with a sex ratio of 0.11 against 0.5 of the control. The results indicate that we must be careful to recommend the evaluated insecticides, observing the persistence of those classified as harmful to A. citricola, as a manner to explore the ecological selectivity. Even though considered harmless to adult parasitoids, abamectin can lead to population reduction of A. citricola, being necessary field studies to confirm that situation.

As escolhas de um predador podem variar de acordo com a abundância da presa no ambiente, atributos físicos e comportamentais da presa e do predador, além do custo energético, resultando na seleção de determinadas presas em detrimento de outras. Os raros estudos de seletividade na dieta da coruja-buraqueira (Athene cunicularia) realizados no Brasil tiveram como foco a seleção de roedores. Por este motivo o presente estudo tem como objetivos, além do estudo quantitativo da dieta, verificar se ocorre seletividade de coleópteros copro-necrófagos por A. cunicularia e se atributos da presa e/ou do predador, além de parâmetros climáticos, podem influenciar na predação e seletividade. Foram utilizados restos de presas (ossos, mandíbulas, cinturas pélvicas, élitros, pronotos e cabeças) encontrados nas pelotas e ao redor dos ninhos nos campos do Cerrado da Estação Ecológica de Itirapina (São Paulo) para identificação das espécies, quantificação do número de indivíduos consumidos e biomassa bruta ingerida. A sazonalidade na dieta foi testada por meio do teste-G de independência (tabela de contingência). Foram calculados os índices de amplitude de nicho trófico de Levins (Bst) para cada coleta, e efetuado o teste de Mann-Whitney para avaliar sazonalidade na amplitude da dieta entre a estação chuvosa e seca. Dados climáticos como temperatura máxima e média, umidade e pluviosidade médias foram relacionados com os números de indivíduos dos grupos predominantes na dieta e no campo por meio da correlação de Pearson. A análise da seleção de besouros escarabeíneos (copro-necrófagos) foi realizada por meio do intervalo de confiança de Bailey. Foram coletadas 421 pelotas e 183 debris que resultaram em 4341 presas individuais e uma biomassa total de 6.184,75 g. A dieta da A. cunicularia numericamente é predominantemente composta por insetos (92,88%), principalmente Coleoptera (48,4%), Orthoptera (10,1%) e Blattaria (16,7%). As famílias mais frequentes de coleópteros foram Scarabaeidae (26,2%) e Carabidae (8,7%). Por outro lado, em termos de biomassa bruta ingerida, os vertebrados foram importantes com 40,20%. Não houve diferenças sazonais na amplitude de nicho trófico (U = 11; p = 0,153), porém ao se considerar as frequências absolutas (número de indivíduos) houve significantemente, maior consumo de insetos (principalmente besouros escarabeídeos) e anuros na estação chuvosa e de roedores na estação seca (G independência = 644,9; g.l. = 11; p < 0,0001). Em alguns casos, a predação e a abundância das presas foram positivas e diretamente relacionadas com a temperatura, umidade e precipitação. Os escarabeíneos foram mais coletados e consumidos com o aumento da temperatura, umidade e pluviosidade médias. A amplitude da dieta para A. cunicularia na EEI foi considerada ampla, apesar dos valores de Bst próximos à zero. As corujas estudadas selecionaram alguns coleópteros copro-necrófagos (Scarabaeidae: Scarabaeinae) encontrados na EEI, selecionando três espécies do gênero Dichotomius (sp. 1, sp. 2 e sp. 3) na estação chuvosa e Dichotomius glaucus, (sp. 1 e sp. 3) e Coprophanaeus ensifer na seca. Estes escarabeídeos podem ser vulneráveis a predação por causa de aspectos de sua biologia, como hábito terrícola, atividade nas horas crepusculares-noturnas, movimento lento, falta de defesa ativa, e tamanho adequado (15-25 mm; 0.8-2.0 g) ao consumo para o porte da coruja-buraqueira. / Predator\'s choice can change according to prey abundance in the environment, physical and behavioral traits both of predator and prey, and energy cost whose influences may result in selection of some prey. The rare prey selection studies of the Burrowing-Owl in Brazil were focused only in small mammals. The aims of this research were to study quantitatively the diet of the Burrowing-Owl and to analyze dung beetle prey selection, searching if any prey and/or predator traits, as well as if climatic parameters may influence on selectivity and predation. Prey remains (bones, mandibles, pelvic girdles, elytron, and heads) found in pellets and in the nest sites at the grasslands of Ecological Station of Itirapina (State of São Paulo, southeast Brazil) were utilized to identify prey species, to quantify number of consumed individuals and ingested biomass. The seasonality in the diet was evaluated by G-test (table of contingency). The index of food niche breadth (Bst) was calculated for each month and its seasonality between rainy and dry season was evaluated by Mann-Whitney\'U-test. Weather variables such as mean figures of maximum and mean temperature, mean precipitation and air relative humidity were analyzed to reveal possible correlations with number of prey items collected in pellets and in the environment. For this analysis the Pearson\'s correlation (r) was calculated. The analysis of dung bettles selection was conducted by Bailey\'s confidence intervals. A total of 421 pellets and 183 debris were collected yielding 4341 prey individuals and 6,184.75 g of estimated biomass. Insects were the most frequent prey in the Burrowing-Owl\'s diet (92.88%), mainly Coleoptera (48.4%), Orthoptera (10.1%) and Blattaria (16.7%). The most frequent beetle families were Scarabaeidae (26.2%) and Carabidae (8.7%). On the other hand, vertebrates were important in terms of biomass (40.20%). There was no seasonality on the food-niche breadth (U = 11, p = 0.153), but by absolute frequencies (number of prey) there was a significantly higher consumption of insects (mainly scarabs) and frogs in the wet season, and rodents in the dry season (G = 644.9; d.f. = 11; p < 0.0001). In some instances predation and abundance of prey had positive and directly proportional correlation with temperature, humidity and rainfall. The dung beetles were more consumed and available in the environment with increasing temperature, humidity and rainfall averages. The food-niche breadth was wide despite of the Bst values near zero. The Burrowing-owl selected some dung beetles (Scarabaeidae: Scarabaeinae) these being Dichotomius (sp. 1, sp. 2 and sp. 3) at rainy and Dichotomius glaucus, (sp. 1 e sp. 3) and Coprophanaeus ensifer at the dry season. These scarabs may be vulnerable because some of its biological traits. Dichotomius are ground medium beetles which forage at twilight/night, and has an adequate size (15-25 mm; 0.8-2.0 g) for the Burrowing-Owl size.

Thesis advisor: Kian L. Tan / Thesis advisor: Shih-Yuan Liu / Chapter 1. In the Tan laboratory, we developed synthetic methods to control reaction selectivity (regio-, stereo-, and site-selectivity) using scaffolding catalysis. Our strategy utilizes directing groups that induce intramolecularity through the formation of a labile covalent bond between the substrate and a binding site in a catalytic system. In the first part, we described site-selective functionalization of various carbohydrates and complex polyhydroxylated molecules which contain cis-1,2-diol motif using a chiral organic scaffold. In the second part, meta-selective C–H functionalization of arenes was demonstrated. High meta-selectivity was achieved by the use of a nitrile-based silyl tether which is cleavable and recyclable. Chapter 2. In the Liu laboratory, we focuses on studies of boron-nitrogen containing heterocycles. In this chapter, synthesis of 1,2-azaborines and their binding study with T4 lysozyme mutants were described. Specifically, we directly compared binding of NH-containing 1,2-azaborines and their carbonaceous analogs to probe hydrogen bonding interaction between the NH group of azaborine and a carbonyl oxygen of protein residue. Structural and thermodynamic analysis provided us the first evidence of H-bonding of azaborines with a biological macromolecule. Chapter 3. Described are the synthesis of regioisomers of ethyl-substituted 1,2-azaborines and their binding thermodynamics to T4 lysozyme mutants. To access the azaborine ligands used in the binding study, we developed synthetic methods for regioselective functionalization of six positions of 1,2-azaborines. Isothermal titration calorimetry experiments showed differences in binding free energy for regioisomers to the L99A T4 lysozyme. This result could originate from electronic differences of the isosteric ligands inducing dipole-dipole interaction between ligand and surrounding protein residues or it may be from local dipolar interactions. Chapter 4. A general method for late-stage N-functionalization of 1,2-azaborines is described to afford libraries of BN-containing complex molecules. The chemical transformations include electrophilic substitution reactions, N–C(sp2) bond forming reactions under Buchwald-Hartwig amination conditions, and N–C(sp) bond forming reactions using copper-catalyzed N-alkynylation. As applications in materials science and medicinal chemistry, synthesis of the first parental BN isostere of trans-stilbene and lisdexamfetamine derivative is described utilizing the methodology developed in this work. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

O controle químico de pragas, para muitas culturas agrícolas é uma das principais táticas em programas de manejo integrado de pragas (MIP), trazendo benefícios reais e diminuindo as perdas por insetos-praga, além do aumento na produção de alimentos e fibras, proteção de produtos armazenados e proteção de pragas e doenças de seres humanos. O controle de pragas em soja e milho tem sido realizado, em sua maioria, utilizando-se plantas Bt e produtos químicos, este último, além das diversas vantagens citadas, pode ter desvantagens, principalmente quando utilizado de maneira inadequada, com potencial de causar diversos problemas no agroecossistema, além de desequilíbrios ambientais. Devido a importância da cultura da soja e do milho para o Brasil e para o mundo, como base da alimentação animal e humana, reconhecendo o grande uso e papel dos inseticidas como uma das principais táticas usadas para o controle de insetos-praga destas culturas, se faz necessário estudos que tratem da melhor forma de uso dos inseticidas e estudos que avaliem possíveis efeitos adversos destas moléculas em insetos benéficos, para que estejam de acordo com as premissas do MIP. Para viabilizar esta importante tática de controle, realizou-se estudos com os seguintes objetivos: 1) Estudar a toxicidade residual dos inseticidas indoxacarb (Avatar&reg;), chlorantraniliprole (Premio&reg;), spinosad (Tracer&reg;) e teflubenzuron (Nomolt 150&reg;) para C. includens em soja, em ensaio com e sem simulação de chuva; 2) Estudar a toxicidade residual dos inseticidas indoxacarb (Avatar&reg;), chlorantraniliprole (Premio&reg;), spinosad (Tracer&reg;) e teflubenzuron (Nomolt 150&reg;) para S. frugiperda em milho, em ensaio com e sem simulação de chuva; 3) Avaliar efeito letal e subletal de inseticidas recomendados para soja e milho sobre o predador Doru luteipes. Para o primeiro objetivo, teflubenzuron (15 g i. a. ha-1); spinosad (36 g i. a. ha-1); chlorantraniliprole (5, 10 e 20 g i. a. ha-1); indoxacarb (30, 60 e 90 g i. a. ha-1) não tiveram a eficácia afetada quando submetidos à simulação de chuva em todos os tempos avaliados. Quanto a toxicidade residual ao longo do tempo, teflubenzuron, chlorantraniliprole e indoxacarb, nas duas condições, com e sem simulação de chuva, tiveram redução da eficácia após o 5° dia. Diferentemente, os inseticidas spinosad (36 g i. a. ha-1) e indoxacarb (90 g i. a. ha-1), nas duas condições, não tiveram redução da eficácia até 15 dias após aplicação, e em todos os tempos avaliados foram mais eficazes do que os demais inseticidas. Para o segundo objetivo, spinosad (36 g i. a. ha-1) e chlorantraniliprole (10, 20 e 30 g i. a. ha-1) mantiveram a eficácia até o 15º dia após pulverização. Quanto aos efeito da simulação da chuva, spinosad (36 g i. a. ha-1), chlorantraniliprole (10, 20 e 30 g i. a. ha-1) e indoxacarb (90 g i. a. ha-1) mantiveram a eficácia. O inseticida chlorantraniliprole na maior dose utilizada e recomenda para o controle da praga na cultura foi o mais efetivo dentre todos, quanto a toxicidade residual e sob ação da simulação de chuva. Quanto ao terceiro objetivo, ensaio de efeito letal, Tracer, Premio e Avatar foram classificados como nocivos (classe 4), e somente Nomolt foi inócuo (classe 1). No ensaio de efeito subletal apenas o inseticida Nomolt teve parâmetros avaliados. Apesar disso, causou efeitos adversos ao predador, como: aumento do período de pré-oviposição; aumento do período embrionário e diminuição da fecundidade; não sendo, portanto, recomendado para utilização em programas de MIP, pois, altera a capacidade de desenvolvimento e reprodutiva da tesourinha predadora. Os resultados obtidos nesses estudos proveram importantes informações para o refinamento do uso de moléculas inseticidas e classificação desses quanto a seletividade ao predador generalista D. luteipes, agregando informações práticas para o manejo de pragas na cultura da soja e milho. / Chemical pest control for many agricultural crops is one of the main tactics in integrated pest management (IPM) programs, bringing real benefits and decreasing losses by pest insects, as well as increased food and fiber production, protection of stored products and protection of pests and diseases of humans. Pest control in soybean and corn has been mostly carried out using Bt plants and chemical products, for the latter, in addition to the several advantages cited, may have some disadvantages, especially when used improperly, with the potential to cause several problems in the agroecosystem, as well as environmental impacts. Owing to the importance of soybean and corn cultivation to Brazil and to the world, as a basis of animal and human feeding, recognizing the great use and role of insecticides as one of the main tactics used to control insect pests of these crops, it is necessary to study the best use of insecticides and studies that evaluate the possible adverse effects of these chemical molecules on beneficial insects, so that they are in accordance with the IPM premises. To enable this important control tactic, studies were carried out with the following objectives: 1) To study the residual toxicity of insecticides indoxacarb (Avatar&reg;), chlorantraniliprole (Premio&reg;), spinosad (Tracer&reg;) and teflubenzuron (Nomolt 150&reg;) for C. includens in soybeans, with and without rainfastness; 2) To study the residual toxicity of insecticides indoxacarb (Avatar&reg;), chlorantraniliprole (Premio&reg;), spinosad (Tracer&reg;) and teflubenzuron (Nomolt 150&reg;) for S. frugiperda in maize, with and without rainfastness; 3) To evaluate the lethal and sublethal effect of insecticides recommended for soybean and corn on the earwing predator Doru luteipes. For the first objective, teflubenzuron (15 g a. i. ha-1); spinosad (36 g a. i. ha-1); chlorantraniliprole (5, 10 and 20 g a. i. ha-1); indoxacarb (30, 60 and 90 g a. i. ha-1) were not affected when submitted to rainfastness at all evaluated times. Concerning for residual toxicity over time, teflubenzuron, chlorantraniliprole e indoxacarb, under both conditions, with and without rainfastness, had a reduction in efficacy after 5 day. In contrast, the insecticides spinosad (36 g a. i. ha-1) and indoxacarb (90 g a. i. ha-1), in both conditions had no efficacy reduction until 15 days after application and at all times evaluated were more effective than the other insecticides. For the second objective, spinosad (36 g a. i. ha-1) e chlorantraniliprole (10, 20 and 30 g a. i. ha-1) maintained efficacy until the 15th day after spraying. As for the effects of rainfastness, spinosad (36 g a. i. ha-1), chlorantraniliprole (10, 20 and 30 g a. i. ha-1) and indoxacarb (90 g a. i. ha-1) remained effective. The insecticide chlorantraniliprole at the highest dose used and recommended for the control of the pest in the crop was the most effective of all, regarding residual toxicity and under the action of the rainfastness. About the third objective, lethal effect bioassay, Tracer, Premio e Avatar were classified as harmful (class 4), and only Nomolt was innocuous (class 1). In the test of sublethal effect, just the insecticide Nomolt had parameters evaluated. Nevertheless, it caused adverse effects to the predator, such as: increased pre-oviposition period; increase in the embryonic period and decrease in fecundity; therefore, it is not recommended for use in IPM programs, because it modify the developmental and reproductive capacity of predatory earwings. The results obtained in these studies provided important information for the refinement of the use of insecticidal molecules and the classification of these as the selectivity to the generalist predator D. luteipes, adding practical information for pest management in soybean and corn crops.

O uso de inseticidas em um agroecossistema pode interferir na densidade e ação dos inimigos naturais e comprometer a eficácia do controle biológico dentro de um programa de manejo integrado de pragas. Dessa forma, objetivou-se avaliar, em laboratório, os efeitos letal e subletais de inseticidas reguladores de crescimento sobre larvas e adultos com até 24 h de idade do predador Ceraeochrysa cubana (Hagen, 1861). Para isso, larvas recém-eclodidas foram submetidas à pulverização de 2 mL de calda, do respectivo tratamento, em torre de Potter ajustada para deposição de 1,8 ± 0,1 mg cm-2. Os inseticidas e doses (g i.a. L-1) avaliados foram: piriproxifem 0,2 (Tiger 100 EC), buprofezina 0,5 (Applaud 250), tebufenozida 0,22 (Mimic 240 SC), metoxifenozida 0,75 (Intrepid 240 SC), diflubenzurom 0,12 (Micromite 240 SC), lufenurom 0,05 (Match EC). Água destilada foi utilizada como tratamento controle. A mortalidade de larvas, pupas e adultos e o número de ovos depositados pelas fêmeas foram avaliados a cada 24 h. A viabilidade de ovos foi determinada a partir da terceira oviposição das fêmeas utilizando 100 ovos de cada indivíduo. Os efeitos letais foram observados em larvas tratadas com diflubenzurom, lufenurom e piriproxifem. Os inseticidas piriproxifem, tebufenozida, metoxifenozida e buprofezina causaram redução na fecundidade de 20 a 40% e na fertilidade de no máximo 10%, sendo considerados levemente nocivos (30<E<=79 de redução), enquanto que, diflubenzurom e lufenurom causaram 100% de mortalidade de larvas de C. cubana e foram considerados nocivos ao predador (E>99%). Não houve diferenças significativas entre os tratamentos quanto aos parâmetros taxa líquida de reprodução (Ro), taxa intrínseca de crescimento (rm) e taxa finita de aumento (?). No entanto, diferenças significativas foram constatadas no tempo médio entre gerações (T), sendo que os menores valores foram constatados nos insetos expostos aos inseticidas tebufenozida e metoxifenozida. No bioensaio com adultos, lufenurom, diflubenzurom reduziram significativamente a fecundidade e fertilidade, enquanto que, tebufenozida, metoxifenozida e buprofezina não diferiram do controle. Piriproxifem reduziu significativamente a fecundidade total, porém, não afetou a fertilidade e a longevidade. Embora inseticidas reguladores de crescimento sejam comumente considerados como seletivos, afetaram a sobrevivência e reprodução de C. cubana em condições de laboratório. Todos os inseticidas testados devem ser submetidos a ensaios de semi-campo o para confirmação dos resultados, entretanto, tebufenozida, metoxifenozida, buprofezina e piriproxifem foram considerados levemente nocivos e, consequentemente, mais indicados para utilização dentro de programas de manejo integrado de pragas envolvendo C. cubana ou outras espécies de crisopídeos. / The use of pesticides within an agricultural system can interfere with the density and functionality of natural enemies, thus endangering the efficacy of biological control in the Integrated Pest Management program. Hence, this study evaluated the lethal and sublethal effects of six Insect Growth Regulators (IGR) insecticides over the larvae and adults of Green Lacewing Ceraeochrysa cubana (Hagen, 1861) under laboratory conditions. Neonate larvae and newly-emerged adults were sprayed with the respective treatments with the aid of a Potter Tower (2 mL of spray solution, 1.8 ± 0.1 mg cm-2 of deposition). The insecticides and rates (g a.i. L-1) evaluated were: pyriproxyfen 0.2 (Tiger 100 EC), buprofezin 0.5 (Applaud 250), tebufenozide 0.22 (Mimic 240 SC), methoxyfenozide 0.75 (Intrepid 240 SC), diflubenzuron 0.12 (Micromite 240 SC), lufenuron 0.05 (Match EC) and for control, distilled water. The mortality of larvae, pupa and adults and the number of eggs laid were registered daily. The viability was assessed by observing the percentage of eclosion from 100 eggs. Lethal effects were observed in larvae treated with diflubenzurom, lufenuron and pyriproxyfen. The insecticides pyriproxyfen, tebufenozide, methoxyfenozide and buprofezin reduced fecundity from 20 to 40% and fertility at highest 10%, being considered slightly harmful (30%<E<79%), whereas diflubenzuron and lufenuron caused 100% of larvae mortality and were considered harmful (E>99%). No significant differences were found among treatments for net reproduction rate (Ro), intrinsic growth rate (rm) and finite rate of increase (?). However, significant differences were found in mean generation time (T) for methoxyfenozide and tebufenozide. For adult bioassay, lufenuron and diflubenzuron reduced significantly the fecundity and fertility, whereas tebufenozide, methoxyfenozide and buprofezin did not differ from control. Pyriproxyfen significantly reduced the fecundity, but, did not affect fertility and longevity. Although IGRs are commonly taken as selective insecticides, they reduced the survivorship and reproduction of C. cubana in laboratory conditions. All products must be directed for semi-field studies for confirmation of results, however, tebufenozide, methoxyfenozide and buprofezin were considered slightly harmful for larvae and, consequently more appropriate to use in Integrated Pest Management programs whenever C. cubana as well as other lacewing species are present.

The endogenous, or voluntary, control of visuospatial attention relies upon interactions within a frontoparietal dorsal attention network (DAN) and this network’s top-down influence on visual occipital cortex (VOC). While these interactions have been shown to occur during attention tasks, they are also known to occur to some extent at rest, but the degree to which task-related interactions reflect either modulation or reorganization of such ongoing intrinsic interactions is poorly understood. In addition, it is known that in spatial neglect—a syndrome following unilateral brain lesions in which patients fail to attend to the contralesional side of space—symptom severity covaries with disruptions to intrinsic interhemispheric interactions between left and right homologous regions of the DAN; however, similar covariance with disruptions to intrahemispheric interactions within the DAN, and between the DAN and VOC, has not been demonstrated. These issues are addressed herein via the measurement of both undirected and directed functional connectivity (UFC, DFC) within the DAN and between the DAN and VOC. UFC and DFC were derived from correlations of, and multivariate vector autoregressive modeling of, fMRI BOLD time-series, respectively. Time-series were recorded from individuals performing an anticipatory visuospatial attention task and individuals at rest, as well as from stroke patients either with or without neglect and age-matched healthy controls. With regard to the first issue, the results show that relative to rest, top-down DAN-to-VOC influence and within-DAN coupling are elevated during task performance, but also that intrinsic connectivity patterns are largely preserved during the task. With regard to the second issue, results show that interhemispheric imbalances of intrahemispheric UFC and DFC both within the DAN and between the DAN and VOC strongly correlate with neglect severity, and may co-occur with functional decoupling of the hemispheres. This work thus demonstrates that the intrinsic functional integrity of the DAN and its relationship to VOC is crucial for the endogenous control of visuospatial attention during tasks, and that the compromise of this integrity due to stroke likely plays a role in producing spatial neglect. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2016. / FAU Electronic Theses and Dissertations Collection

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