Computational methods have been extensively developed at various levels of approximation in recent years to model biomolecular interactions and for rational drug design. This research work aims to explore the feasibility of using quantum mechanical (QM) methods within the two broad categories of in silico ligand-based and structure-based drug design. First, density functional theory at the M06L level of theory was employed to examine structure-activity relationships of boron-based heterocyclic compounds, anti-inflammatory inhibitors targetting the interleukin-1β (IL-1β) cytokine. Our findings from computed energies and shapes of the molecular orbitals provide understanding of electronic effects associated with the inhibitory activity. We also found that the boron atom, specifically its electrostatic polarity, appears to be essential for the anti-IL-1β activity as evidenced by the biological assay of non-boron analogues selected from the ligand-based virtual screening results. Secondly, we aimed to dock ligands at the active sites of zinc-containing metalloproteins with reasonable computational cost and with accuracy. Therefore, an in-house docking scheme based on a Monte Carlo sampling algorithm using the semiempirical PM6/AMBER force field scoring function was compiled for the first time within the Gaussian 09 program. It was applied to four test cases, docking to cytidine deaminase and human carbonic anhydrase II proteins. The docking results show the method’s promise in resolving false-positive docking poses and improving the predicted binding modes over a conventional docking scheme. Finally, semiempirical QM methods which include dispersion and hydrogen-bond corrections were assessed for modelling conformations of β-cyclodextrin (βCD) and their adsorption on graphene. The closed in vacuo βCD cccw conformer was found to be in the lowest energy, in good agreement with previous ab initio QM studies. DFTB3, PM6-DH2 and PM7 methods were applied to model the intermolecular interactions of large βCD/graphene complexes, over a thousand atoms in size. We found that the binding preference of βCD on graphene is in a closed conformation via its C2C3 rim, agreeing with reported experimental and computational findings.

Objetivando-se estudar o efeito de métodos químicos de indução de copa no desenvolvimento da seringueira, realizou-se experimento em condições de campo, em Casa Branca-SP, aplicando-se reguladores vegetais de crescimento em plantas enxertadas do cultivar RRIM 600 com 20 meses de idade, com 1,70 a 3,00 m de altura e último lançamento foliar maduro. O experimento foi delineado em Blocos ao Acaso com quatro repetições, utilizando-se como tratamentos, a aplicação de hidrazida maléica a 500, 750 e 1. 000 ppm, chlormequat a 1.000, 1.500 e 2.000 ppm, daminozide a 2.000, 3.000 e 4.000 ppm e a testemunha. Durante a realização do experimento efetuaram-se avaliações das seguintes variáveis: perímetro do tronco, espessura de casca, altura da árvore, altura do tronco, comprimento da copa, diâmetro da copa, número e porcentual de árvores ramificadas, número de ramos, concentração de ramos, ângulo de inserção dos ramos, índice de área foliar, coeficiente de absorção de radiação e danos por vento. Estudos de correlação foram feitos para analisar a influência das características da copa sobre o desenvolvimento das árvores. Nas condições em que foi conduzido o experimento, os resultados obtidos permitiam concluir que a indução de copa por métodos químicos pode incrementar o crescimento do perímetro do tronco, reduzindo o período de imaturidade da seringueira e que a injúria ou morte da gema apical aumentam a susceptibilidade das copas a danos por vento. O melhor tratamento foi com daminozide a 2.000 ppm, que apresentou ganho de 25% no perímetro relativo do tronco em relação à testemunha. Os tratamentos com daminozide apresentaram ganhos em perímetro do tronco sem comprometer a resistência das copas a danos por vento. Os tratamentos com chlormequat e hidraliza maléica não apresentaram ganhos em perímetro do tronco sendo que o último comprometeu a resistência das copas a danos por vento. O perímetro do tronco está positivamente correlacionado com a altura da árvore, o comprimento da copa, o diâmetro médio da copa e a espessura de casca; e negativamente relacionado com a altura do tronco. / This study describes the influences of chemical methods of branch induction on growth of Hevea brasiliensis. The experiment was situated in Casa Branca-SP, Brazil, where growth regulators were sprayed on buddings of cultivar RRIM 600, 20 months after planting. The experiment was delineated in randon blocks with 4 repetitions with the following treatments: maleic hydrazide at 500, 750 and 1,000 ppm; chlormequat at 1,000, 1,500 and 2,000 ppm; daminozide at. 2,000, 3,000 and 4,000 ppm, and control. Tree girth, bark thickness, tree and crown height, crown length, crown width, branch number and concentration, branch slope, leaf area index, canopy light absorption and wind damage measurements were carried out at regular intervals, during experiment period. Correlation studies were made to explain the relationships between canopy characters and tree growth. Under the prevailing experimental conditions we may derive the following conclusions: branch induction by chemical methods may increase the tree girth, reducing immature period of rubber; injury to the terminal apex increases susceptibility to wind damage; the best treatment was daminozide at 2,000 ppm presenting 25% gain on tree girth compared to control; daminozide treatments enhanced tree girth without changing the wind damage susceptibility; chlormequat and maleic hydrazide treatments did not increase tree girth, and the latest reduced the crowns wind damage resistance; tree girth is positive correlated with tree height, crown length, crown width and bark thickness, and negative correlated with crotch height.

Objetivando-se estudar o efeito de métodos químicos de indução de copa no desenvolvimento da seringueira, realizou-se experimento em condições de campo, em Casa Branca-SP, aplicando-se reguladores vegetais de crescimento em plantas enxertadas do cultivar RRIM 600 com 20 meses de idade, com 1,70 a 3,00 m de altura e último lançamento foliar maduro. O experimento foi delineado em Blocos ao Acaso com quatro repetições, utilizando-se como tratamentos, a aplicação de hidrazida maléica a 500, 750 e 1. 000 ppm, chlormequat a 1.000, 1.500 e 2.000 ppm, daminozide a 2.000, 3.000 e 4.000 ppm e a testemunha. Durante a realização do experimento efetuaram-se avaliações das seguintes variáveis: perímetro do tronco, espessura de casca, altura da árvore, altura do tronco, comprimento da copa, diâmetro da copa, número e porcentual de árvores ramificadas, número de ramos, concentração de ramos, ângulo de inserção dos ramos, índice de área foliar, coeficiente de absorção de radiação e danos por vento. Estudos de correlação foram feitos para analisar a influência das características da copa sobre o desenvolvimento das árvores. Nas condições em que foi conduzido o experimento, os resultados obtidos permitiam concluir que a indução de copa por métodos químicos pode incrementar o crescimento do perímetro do tronco, reduzindo o período de imaturidade da seringueira e que a injúria ou morte da gema apical aumentam a susceptibilidade das copas a danos por vento. O melhor tratamento foi com daminozide a 2.000 ppm, que apresentou ganho de 25% no perímetro relativo do tronco em relação à testemunha. Os tratamentos com daminozide apresentaram ganhos em perímetro do tronco sem comprometer a resistência das copas a danos por vento. Os tratamentos com chlormequat e hidraliza maléica não apresentaram ganhos em perímetro do tronco sendo que o último comprometeu a resistência das copas a danos por vento. O perímetro do tronco está positivamente correlacionado com a altura da árvore, o comprimento da copa, o diâmetro médio da copa e a espessura de casca; e negativamente relacionado com a altura do tronco. / This study describes the influences of chemical methods of branch induction on growth of Hevea brasiliensis. The experiment was situated in Casa Branca-SP, Brazil, where growth regulators were sprayed on buddings of cultivar RRIM 600, 20 months after planting. The experiment was delineated in randon blocks with 4 repetitions with the following treatments: maleic hydrazide at 500, 750 and 1,000 ppm; chlormequat at 1,000, 1,500 and 2,000 ppm; daminozide at. 2,000, 3,000 and 4,000 ppm, and control. Tree girth, bark thickness, tree and crown height, crown length, crown width, branch number and concentration, branch slope, leaf area index, canopy light absorption and wind damage measurements were carried out at regular intervals, during experiment period. Correlation studies were made to explain the relationships between canopy characters and tree growth. Under the prevailing experimental conditions we may derive the following conclusions: branch induction by chemical methods may increase the tree girth, reducing immature period of rubber; injury to the terminal apex increases susceptibility to wind damage; the best treatment was daminozide at 2,000 ppm presenting 25% gain on tree girth compared to control; daminozide treatments enhanced tree girth without changing the wind damage susceptibility; chlormequat and maleic hydrazide treatments did not increase tree girth, and the latest reduced the crowns wind damage resistance; tree girth is positive correlated with tree height, crown length, crown width and bark thickness, and negative correlated with crotch height.

Alkali-silica reaction (ASR) is a common deterioration mechanism responsible for numerous concrete durability issues. Since ASR was first discovered in the 1940's, a significant number of investigations have been carried out in order to understand its mechanisms. However, due to the complexity of the reaction and to the numerous factors that affect its development, many aspects still remain unexplained. The research described in this document was funded by the Texas Department of Transportation (TxDOT), and it focused on a specific type of reactive aggregates, known as 'pessimum'; they present an unexpected behavior with respect to the relation between the amount of material present in the mixture and the extent of ASR related damage. The main objective of this investigation was to determine a method for identifying aggregates that exhibit the 'pessimum' behavior by means of a short-term testing regime. Modified versions of the Accelerated Mortar Bar Test (AMBT) and the Concrete Microbar Test (CMBT) were considered for this purpose. In addition, the behavior of a selected group of 'pessimum' aggregates in the Concrete Prism Test (CPT) and the Chemical Method was evaluated. The petrographic characteristics for a reduced number of the aggregates studied were linked to their performance in the ASR tests. The results obtained from the experimental program conducted were combined with results from previous investigations performed at UT Austin to draw conclusions about the overall behavior of ‘pessimum’ aggregates. ‘Pessimum’ aggregates were successfully identified with a modification proposed to the AMBT. As for their behavior, it was found that depending on the amount of reactive constituents present in each test, these aggregates are classified as reactive (for low chert contents) or as non-reactive (for chert contents above the 'pessimum' proportion). Whether these aggregates will generate durability problems depends on the amount of reactive silica in the concrete mixture. / text