Stereochemical and electronic interaction studies of some N-methoxy-N-methyl-2-[(4 `-substituted)phenylsulfinyl]propanamides

The (1)H NMR spectra of N-methoxy-N-methyl-2-[(4`-substituted)phenylsulfinyl]-propanamides [Y-Ph-S(O)CH(Me)C(O)N(OMe)Me; Y = OMe 1, Me 2, H 3. Cl 4, NO(2) 5] along with the X-ray diffraction analysis of the nitro-derivative (5). have shown the existence of two pairs of diastereomers (racemic mixture) [C(R)S(S)/C(S)S(R) (diast(1)) and C(R)S(R)/C(S)S(S) (diast(2))] in the ratio of ca. 7:3. respectively. The v(CO) IR analysis of the title compounds supported by HF and B3LYP/6-31G** calculations of 3 and of the parent N-methoxy-N-methyl-propanamide (6) by HF, have shown that diast(1) exists in an equilibrium between the two more polar and more stable quasi-cis (q-c(1) and q-c(2)) conformers and the gauche(g) conformer. The population of the g conformer in the equilibrium increases with the increase in the solvent polarity, which is attributed to a larger solvation effect on the carbonyl and sulfinyl groups. Diast(2) of compound 3 occurs in the gas phase as an equilibrium between the most stable quasi-gauche (q-g) conformer and the quasi-cis (q-c) conformer, both presenting very similar dipole moments. The former is stabilized by electrostatic and charge transfer interactions, which results in a less solvated spatial arrangement. Moreover, all conformers of both diastereomers are stabilized by several intramolecular hydrogen bonds. X-ray single crystal analysis performed for diast(1) and for diast(2) of 5 indicates that both stereoisomers assume, in the solid state, the anti-clinal (gauche) conformation. For the crystal packing, diast(1) of 5 is made up of three molecules joined through two centro-symmetric H center dot center dot center dot O hydrogen bonds. (C) 2008 Elsevier B.V. All rights reserved.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Structural and Electronic Properties of Dipyridamole and Derivatives

Quantum mechanical calculations at the B3LYP theory level, together with the 6-31G* basis set, were employed to obtain the energy, ionization potential, and polarizabilites for dipyridamole and derivatives, which are compared with their biological activity. Density functional calculations of the spin densities were performed for radical formed by electron abstraction of dipyridamole and derivatives. The unpaired electron remains in dipyridamole is localized on the nitrogen atoms in the substituent positions 1, 3, 5, 7, 11, 12, 13, 14, with participation of the 9 and 10 carbons in the pyrimido-pyrimidine ring. The antioxidant activity is related with ionization potential, polarizability and Log P.

The SUMA Project: Integrating Observational Data Assessment into Space and Service Design

This presentation was offered as part of the CUNY Library Assessment Conference, Reinventing Libraries: Reinventing Assessment, held at the City University of New York in June 2014.

The risk-properties of human capital and the design of government policies

Whether human capital increases or decreases wage uncertainty is an open question from an empirical standpoint. Yet, most policy prescriptions regarding human capital formation are based on models that impose riskiness on this type of investment. In a two period and finite type optimal income taxation problem we derive prescriptions that are robust to the risk characteristics of human capital: savings should be discouraged, human capital investments encouraged and both types of investment driven to an efficient level from an aggregate perspective. These prescriptions are also robust to the assumptions regarding what choices are observed, despite policy instruments being not.

Brazil and Turkey, a comparative analysis of both countries' economic development and institutional design from the Great Depression to the early 21st century

Apos uma década de rápido crescimento econômico na primeira década do século 21, Brasil e Turquia foram considerados duas das economias emergentes mais dinâmicas e promissoras. No entanto, vários sinais de dificuldades econômicas e tensões políticas reapareceram recentemente e simultaneamente nos dois países. Acreditamos que esses sinais e a sua simultaneidade podem ser entendidos melhor com um olhar retrospectivo sobre a história econômica dos dois países, que revela ser surpreendentemente paralela. Numa primeira parte, empreendemos uma comparação abrangente da história econômica brasileira e turca para mostrar as numerosas similaridades entre os desafios de política econômica que os dois países enfrentaram, assim como entre as respostas que eles lhes deram desde a virada da Grande Depressão até a primeira década do século 21. Essas escolhas de política econômica comuns dão forma a uma trajetória de desenvolvimento notavelmente análoga, caracterizada primeiro pela adoção do modelo de industrialização por substituição das importações (ISI) no contexto da recessão mundial dos anos 1930; depois pela intensificação e crise final desse modelo nos anos 1980; e finalmente por duas décadas de estabilização e transição para um modelo econômico mais liberal. Numa segunda parte, o desenvolvimento das instituições econômicas e políticas, assim como da economia política subjacente nos dois países, são analisados comparativamente a fim de prover alguns elementos de explicação do paralelo observado na primeira parte. Sustentamos que o marco institucional estabelecido nos dois países durante esse período também têm varias características fundamentais em comum e contribui a explicar as escolhas de política econômica e as performances econômicas comparáveis, detalhadas na primeira parte. Este estudo aborda elementos do contexto histórico úteis para compreender a situação econômica e política atual nos dois países. Potencialmente também constitui uma tentativa de considerar as economias emergentes numa perspectiva histórica e comparativa mais ampla para entender melhor as suas fraquezas institucionais e adotar um olhar mais equilibrado sobre seu potencial econômico.

Antecedents of e-loyalty and electronic word-of-mouth

O objetivo principal da dissertação foi o de examinar a relação entre lealdade (e-loyalty) e o boca-a-boca (eWOM) no contexto do varejo eletrônico. Como objetivo secundário, foi feito uma verificação da significância das variáveis preditoras de e-loyalty. Essa pesquisa foi focada em um tipo de produto/serviço: compra de livros através da internet. Duzentos e quarenta e dois questionários online foram respondidos por um público representativo da geração Y (millennials), e rresidentes em diferentes localidades no Brasil e nos Estados Unidos. A análise de dados foi efetuada pela aplicação do método PLS-SEM sobre um modelo de pesquisa cuidadosamente formulado com base em resultados empíricos prévios. Enquanto que a relação entre e-loyalty e eWOM foi classificada como fraca, um ambiente de boca-a-boca online de alta qualidade representou uma variável preditora significativa para o sentimento de e-loyalty. Todas as variáveis preditoras foram classificadas como significativas nesse estudo, sendo que comprometimento tem o efeito mais forte sobre a variável e-loyalty.

Hovercraft telemanipulation virtual models and interface design

A control system was designed to allow humans to manually drive an, usually automatic, two wheeled hovercraft. The size, the mass and the way of driving this vehicle proves to be an issue for the everyday, untrained person to achieve. During this thesis several control layouts were designed with the objective of creating an intuitive and easy way of driving such a vehicle. At the end two where usertested using a simulation (also developed during this thesis) of the said hovercraft set against obstacles similar to those expected to be encountered on its real environment. The two layouts are just slightly apart in performance but numerous issues were found that can be used to redesign a better control layout. This means that no definitive winner was found but a foundation for a better design was indeed found.

Coupling Surface-Enhanced Resonance Raman Scattering and Electronic Tongue as Characterization Tools to Investigate Biological Membrane Mimetic Systems

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanostructured hybrid films containing nanophosphor: Fabrication and electronic spectral properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural and Electronic Effects of Incorporating Mn in TiO2 Films Grown by Sputtering: Anatase versus Rutile

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Periodic study on the structural and electronic properties of bulk, oxidized and reduced SnO2(110) surfaces and the interaction with O-2

The structural and electronic properties of bulk and both oxidized and reduced SnO2(110) surfaces as well as the adsorption process of O-2 on the reduced surface have been investigated by periodic DFT calculations at B3LYP level. The lattice parameters, charge distribution, density of states and band structure are reported for the bulk and surfaces. Surface relaxation effects have been explicitly taken into account by optimizing slab models of nine and seven atomic layers representing the oxidized and reduced surfaces, respectively. The conductivity behavior of the reduced SnO2(110) surface is explained by a distribution of the electrons in the electronic states in the band gap induced by oxygen vacancies. Three types of adsorption approaches of O-2 on the four-fold tin at the reduced SuO(2)(110) surface have been considered. The most exothermic channel corresponds to the adsorption of O-2 parallel to the surface and to the four-fold tin row, and it is believed to be associated with the formation of a peroxo O-2(2-) species. The chemisorption of O-2 on reduced SnO2(110) surface causes a significant depopulation of states along the band gap and it is shown to trap the electrons in the chemisorbed complex producing an electron-depleted space-charge layer in the inner surface region of the material in agreement with some experimental evidences. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Thermodynamic and electronic study of Ga-1 _ xMnxN films. A theoretical study

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optical and mechanical design of an ophthalmic instrument: Slit lamp

This work has as objective to develop an interesting research line in the Optical Instrumentation area, that is to associate the Optical Design to the Ophthalmology area. The purpose of it is handling the optical design techniques to design a widely used ophthalmologic instrument called slit lamp. The optical and mechanical design of the slit lamp prototype was carefully projected in order to improve the best quality image, the comfort of the patient and the user, the simplicity of handling, the facility of production the availability of optical and mechanical components in the national market and the low cost of production. The main goal of this work was to realize a project using totally national technology, cheapening the cost and forming the optimum image required for the slit lamp optical system.