Spectroscopic and theoretical studies of some N,N-diethyl-2-[(4 `-substituted)phenylsulfonyl]acetamides

The analysis of the IR carbonyl band of the N,N-diethyl-2-[(4`-substituted)phenylsulfonyl]acetamides Et(2)NC(O)CH(2)S(O)(2)-C(6)H(4)-Y (Y = OMe 1, Me 2,1-13, Cl 4, Br 5, NO(2) 6) supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three pairs (anti and syn) of cis (c) and gauche (g(1) and g(2)) conformers in the gas phase, being the gauche conformers significantly more stable than the cis ones. The anti geometry is more stable than the syn one, for each pair of cis and gauche conformers. The summing up of the orbital (NBO analysis) and electrostatic interactions justifies quite well the populations and the v(CO) frequencies of the anti and syn pairs of c, g(1) and g(2) conformers. The IR higher carbonyl frequency component whose population is ca. 10%, in CCl(4), may be ascribed to the least stable and most polar cis conformer pair (in the gas phase) and the lower frequency component whose population is ca. 90%, to the summing up of the populations of the two most stable and least polar gauche conformer pairs (g(1) and g(2)) (in the gas phase). The reversal of the cis(c)/gauche (g(1) + g(2)) population ratio observed in chloroform ca. 60% (cis)/40% (gauche) and the occurrence of the most polar cis(c) conformer only, in acetonitrile, strongly suggests the coalescence of the two gauche components in a unique carbonyl band in solution. A further support to this rationalization is given by the single point PCM solvation model performed by HF/6-31G(d,p) method, which showed a progressive increase of the c/(g(1) + g(2)) ratio going from gas to CCl(4), to CHCl(3) and to CH(3)CN. X-ray single crystal analysis of 4 indicates that this compound assumes, in the solid state, the syn-clinal (gauche) conformation with respect to the [O=C-CH(2)-S] moiety, and the most stable anti geometry relative to the [C(O)N(CH(2)CH(3))(2)] fragment. In order to obtain larger energy gain from the crystal packing the molecules of 4 are linked in centrosymmetric dimers through two C-H center dot center dot center dot O interactions (C-H([O-Ph])center dot center dot center dot O([SO2])) forming a step ladder. (C) 2011 Elsevier B.V. All rights reserved.

Conformational preferences for some 2-substituted N-methoxy-N-methylacetamides through spectroscopic and theoretical studies

The analysis of the IR carbonyl band of the 2-substituted N-methoxy-N-methylacetamides Y-CH(2)C(O)-N(OMe)Me (Y = F1, OMe 2, OPh 3, Cl 4), supported by B3LYP/6-311++G(3df, 3pd) calculations along with the NBO analysis for 1-4, indicated the existence of cis-gauche conformers i.e. (c) and (g) for 1 and 3, (c(1), c(2)) and (g(1), g(2)) for 2, and (c) and (g(1), g(2)) for 4. In the gas phase, the g conformer population prevails over the c one, for 1 and 3, the (c(1) + c(2)) population prevails over the (g(1) + g(2)) one for 2, and the (g(1) + g(2)) conformer population is more abundant than (c) one for 4. In n-hexane solution, the cis conformer is more abundant for 1-3. The occurrence of Fermi resonance in the nu(CO) region, in n-hexane, precludes the estimative of relative populations of the (c, g(1), g(2)) conformers for 4. The SCI-PCM calculations agree with the solvent effect on the nu(CO) band component relative intensities for 1-3. NBO analysis showed that the n(N) -> pi.(CO), orbital interaction is the main factor which stabilizes the gauche (g, g(1), g(2)) conformers for 1-4 into a larger extent relative to the cis (c, c(1), c(2)) ones. The n(y) -> pi(.)(Co,) sigma(C-Y) -> pi.(CO,) pi(CO) -> sigma(C-Y) and 7co orbital interactions still contribute, but into a minor extent for the stabilization of the gauche conformers relative to the cis ones. The existence of some pyramidalization at the nitrogen atom of the Weinreb amides 1-4 is responsible for the occurrence of Y(delta)-(4)center dot center dot center dot O(delta)-(9) and Y(delta)-(4)center dot center dot center dot N(delta)-(7) short contacts in the gauche (g, g(1), g(2)) conformers, which originates strong repulsive Coulombic interactions, acting in opposition to the large orbital stabilization of the gauche conformer with respect to the cis one. Therefore, a delicate balance of the Coulombic and orbital interactions seems to be responsible for the observed stabilization of the gauche (g, g(1), g(2)) and cis (c, c(1), c(2)) conformers, both in the gas phase and in the solution for 1-4. However, the cis conformer predominance, in non polar solvents, for the 2-substituted N-methoxy-N-methyl acetamides 1-3, bearing in a first raw (fluorine and oxygen) atoms, is in the opposite direction to the gauche conformer preference for the corresponding 2-substituted N,N-dialkyl-acetamides. (C) 2010 Elsevier B.V. All rights reserved.

Electrocatalysis of ethanol oxidation on Pt monolayers deposited on carbon-supported Ru and Rh nanoparticles

Pt monolayers deposited on carbon- supported Ru and Rh nanoparticles were investigated as electrocatalysts for ethanol oxidation. Electronic features of the Pt monolayers were studied by in situ XANES (X-ray absorption near-edge structure). The electrochemical activity was investigated by cyclic voltammetry and cronoamperometric experiments. Spectroscopic and electrochemical results were compared to those obtained on carbon-supported Pt-Ru and Pt-Rh alloys, and Pt E-TEK. XAS results indicate a modification of the Pt 5d band due to geometric and electronic interactions with the Ru ant Rh substrates, but the effect of withdrawing electrons from Pt is less pronounced in relation to that for the corresponding alloys. Electrochemical stripping of adsorbed CO, which is one of the intermediates, and the currents for the oxidation of ethanol show faster kinetics on the Pt monolayer deposited on Ru nanoparticles, and an activity that exceeds that of conventional catalysts with much larger amounts of platinum. (c) 2007 Elsevier B.V. All rights reserved.

On testing the Phillips curves, the IS Curves, and the interaction between fiscal and monetary policies

Esta tese é composta por três ensaios sobre testes empíricos de curvas de Phillips, curvas IS e a interação entre as políticas fiscal e monetária. O primeiro ensaio ("Curvas de Phillips: um Teste Abrangente") testa curvas de Phillips usando uma especificação autoregressiva de defasagem distribuída (ADL) que abrange a curva de Phillips Aceleracionista (APC), a curva de Phillips Novo Keynesiana (NKPC), a curva de Phillips Híbrida (HPC) e a curva de Phillips de Informação Rígida (SIPC). Utilizamos dados dos Estados Unidos (1985Q1--2007Q4) e do Brasil (1996Q1--2012Q2), usando o hiato do produto e alternativamente o custo marginal real como medida de pressão inflacionária. A evidência empírica rejeita as restrições decorrentes da NKPC, da HPC e da SIPC, mas não rejeita aquelas da APC. O segundo ensaio ("Curvas IS: um Teste Abrangente") testa curvas IS usando uma especificação ADL que abrange a curva IS Keynesiana tradicional (KISC), a curva IS Novo Keynesiana (NKISC) e a curva IS Híbrida (HISC). Utilizamos dados dos Estados Unidos (1985Q1--2007Q4) e do Brasil (1996Q1--2012Q2). A evidência empírica rejeita as restrições decorrentes da NKISC e da HISC, mas não rejeita aquelas da KISC. O terceiro ensaio ("Os Efeitos da Política Fiscal e suas Interações com a Política Monetária") analisa os efeitos de choques na política fiscal sobre a dinâmica da economia e a interação entre as políticas fiscal e monetária usando modelos SVARs. Testamos a Teoria Fiscal do Nível de Preços para o Brasil analisando a resposta do passivo do setor público a choques no superávit primário. Para a identificação híbrida, encontramos que não é possível distinguir empiricamente entre os regimes Ricardiano (Dominância Monetária) e não-Ricardiano (Dominância Fiscal). Entretanto, utilizando a identificação de restrições de sinais, existe evidência que o governo seguiu um regime Ricardiano (Dominância Monetária) de janeiro de 2000 a junho de 2008.

Does absorptive capacity affect project performance? A study based on project management practices, organization learning, and knowledge

The literature has emphasized that absorptive capacity (AC) leads to performance, but in projects its influences still unclear. Additionally, the project success is not well understood by the literature, and AC can be an important mechanism to explain it. Therefore, the purpose of this study is to investigate the effect of absorptive capacity on project performance in the construction industry of São Paulo State. We study this influence through potential and realized absorptive capacity proposed by Zahra and George (2002). For achieving this goal, we use a combination of qualitative and quantitative research. The qualitative research is based on 15 interviews with project managers in different sectors to understand the main constructs and support the next quantitative phase. The content analysis was the technique used to analyze those interviews. In quantitative phase through a survey questionnaire, we collected 157 responses in the construction sector with project managers. The confirmatory factor analysis and hierarchical linear regression were the techniques used to assess the data. Our findings suggest that the realized absorptive capacity has a positive influence on performance, but potential absorptive capacity and the interactions effect have no influence on performance. Moreover, the planning and monitoring have a positive impact on budget and schedule, and customer satisfaction while risk coping capacity has a positive impact on business success. In academics terms, this research enables a better understanding of the importance of absorptive capacity in the construction industry and it confirms that knowledge application in processes and routines enhances performance. For management, the absorptive capacity enables the improvements of internal capabilities reflected in the increased project management efficiency. Indeed, when a company manages project practices efficiently it enhances business and project performance; however, it needs initially to improve its internal abilities to enrich processes and routines through relevant knowledge.

A prospective study on the dimensions of global brands, brand equity and brand value

This doctoral thesis is about global brands under several perspectives, starting this study with and overview on the matter, followed by a "step ahead" in the conceptualization of brand equity and brand value. As the global marketplace dynamically increases, there are theoretical and empirical challenges concerning the global brands that ask for more branding researches, trying to tune and to contextualize meanings and attributes. Thereafter, the thesis intends to provide a discussion about the industry and country-of-origin effects (and their interactions) on the brand value and the firm market value. Finally, the thesis offers an interesting comparison about the practitioners’ perspectives on the dimensions of global brands, the brand equity and the brand value, branding and marketing, including highlights on the brand internationalization process. The thesis offers a general approach on the extant literature in the first chapter, and a specific literature review for each other chapter.

Touch ‘n’ sketch: pen and fingers on a multi-touch sketch application for tablet PC’s

In many creative and technical areas, professionals make use of paper sketches for developing and expressing concepts and models. Paper offers an almost constraint free environment where they have as much freedom to express themselves as they need. However, paper does have some disadvantages, such as size and not being able to manipulate the content (other than remove it or scratch it), which can be overcome by creating systems that can offer the same freedom people have from paper but none of the disadvantages and limitations. Only in recent years has the technology become massively available that allows doing precisely that, with the development in touch‐sensitive screens that also have the ability to interact with a stylus. In this project a prototype was created with the objective of finding a set of the most useful and usable interactions, which are composed of combinations of multi‐touch and pen. The project selected Computer Aided Software Engineering (CASE) tools as its application domain, because it addresses a solid and well‐defined discipline with still sufficient room for new developments. This was the result from the area research conducted to find an application domain, which involved analyzing sketching tools from several possible areas and domains. User studies were conducted using Model Driven Inquiry (MDI) to have a better understanding of the human sketch creation activities and concepts devised. Then the prototype was implemented, through which it was possible to execute user evaluations of the interaction concepts created. Results validated most interactions, in the face of limited testing only being possible at the time. Users had more problems using the pen, however handwriting and ink recognition were very effective, and users quickly learned the manipulations and gestures from the Natural User Interface (NUI).

The Pair-Bond Formation and Its Role in the Stimulation of Reproductive Function in Female Common Marmosets (Callithrix jacchus)

SILVA, H.P.A.; SOUSA, M.B.C. The pair-bond formation and its role in the stimulation of reproductive function in female common marmosets (collithrix Jacchus). International Journal of Primatology, v, 18, n.3, p.387-400, 1997.

Ação de polissacarídeos sulfatados de Fucus Vesiculosus na Hemostasia e no sistema complemento

Fucans are a family of sulfated homo and teropolysaccharides respectively, composed mainly of a- (1®2) and a- (1®3) linked by L-fucose residues. Properties such as the ability to act as an anti-contraceptive, to reduce cholesterol levels, and to act as an anti-tumor agent are much related. We have focused our attention on the anticoagulant properties, platelet aggregation, hemorrhagic activity and complement system in vitro of commercial fucoidan (F) and their purified fractions (F1, F2 and F3) from Fucus vesiculosus obtained from fractionation of the fucoidan with different concentrations of acetone 1, 2 and 3v. These compounds were chemically characterized and the fucoidan (F) was modified by desulfation. The anticoagulant activity of the compounds was assessment by activated partial thromboplastin time (APTT) and prothrombine time assay (PT) using citrated normal human plasma. The results of APPT test showed that F, F1 and F2 have high anticoagulants activities 240.0 s (5 µg). The F3 showed 73.7 s in the same concentrations. The results obtained with PT test to F, F1, F2 and F3 were 81.5 s, 120.0 s, 57.1 and 32.5 s respectively with 50 µg. The dessulfated polymer showed a decrease in the anticoagulant activity in these two tests. Platelet aggregation assay was measured turbidimetrically with platelet aggregometer by method of Born. The aggregation platelet with F and fractions F1, F2 and F3 exhibited a two-phase answer in the concentration of 5 mg/mL with maximum aggregation of 76.36 ± 10.3% ; 69.54 ± 9.40%; 75.94 ± 9.01%; 51.13 ± 9.59% respectively. However, was observed a hipoaggregate profile F (15.17 ± 5.2%), F1 (7.40 ± 3.04 %), F2 (19.1 ± 5.41%) and F3 (5.09 ± 3.02%) at 0.1 mg/mL. The hemorrhagic activity assay was carried in Wistar rats and showed that these compounds have low hemorrhagic effect when compared to heparin. The complement system ( alternative pathway was made using non-sensibilized rabbit red blood cells The results of complement system essay showed that F , F2 and F3 have action inhibitory in relation to the group control 0.544, 0.697, 0.622 and 0.958 respectively The results showed that these compounds have action on this system. Interaction of the polisaccharides with proteins C3 and C4 showed that the fraction F1 stimulated the activity assay hemolytic using red blood cells

Accumulation of six metals in the mangrove crab Ucides cordatus (Crustacea: Ucididae) and its food source, the red mangrove Rhizophora mangle (Angiosperma: Rhizophoraceae)

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

Effect of steeping conditions (sulfur dioxide, lactic acid, and temperature) on starch yield, starch quality, and germ quality from the Intermittent Milling and Dynamic Steeping process (IMDS) for a Brazilian corn hybrid

Effect of lactic acid, SO2, temperature, and their interactions were assessed on the dynamic steeping of a Brazilian dent corn (hybrid XL 606) to determine the ideal relationship among these variables to improve the wet-milling process for starch and corn by-products production. A 2x2x3 factorial experimental design was used with SO2 levels of 0.05 and 0.1% (w/v), lactic acid levels of 0 and 0.5% (v/v), and temperatures of 52, 60, and 68degreesC. Starch yield was used as deciding factor to choose the best treatment. Lactic acid added in the steep solution improved the starch yield by an average of 5.6 percentage points. SO2 was more available to break down the structural protein network at 0.1% than at the 0.05% level. Starch-gluten separation was difficult at 68degreesC. The lactic acid and SO2 concentrations and steeping temperatures for better starch recovery were 0.5, 0.1, and 52degreesC, respectively. The Intermittent Milling and Dynamic Steeping (IMDS) process produced, on average, 1.4% more starch than the conventional 36- hr steeping process. Protein in starch, oil content in germ, and germ damage were used as quality factors. Total steep time can be reduced from 36 hr for conventional wet-milling to 8 hr for the IMDS process.

Species Diversity of Myrmecofauna and Araneofauna Associated with Agroecosystem and Forest Fragments and their Interaction with Carabidae and Staphylinidae (Coleoptera)

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

Transcriptomics and systems biology analysis in identification of specific pathways involved in cacao resistance and susceptibility to witches' broom disease

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Ab initio study and NMR analysis of the complexion of citric acid with ion lithium

Quantum mechanics calculations at the ab initio HF/3-21G* level were carried out with Nuclear Magnetic Resonance (NMR) measurements to characterize citric acid and lithium interactions. The results indicate the formation of a tridentate organometallic compound with one lithium and one citric acid molecule and a tridentate and bidentate compound of two lithium atoms and one citric acid molecule. The results are in agreement with the experimental and theoretical data. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Influence of Different Base Thicknesses on Maxillary Complete Denture Processing: Linear and Angular Graphic Analysis on the Movement of Artificial Teeth

Objective: The purpose of this study was to compare the dental movement that occurs during the processing of maxillary complete dentures with 3 different base thicknesses, using 2 investment methods, and microwave polymerization.Methods: A sample of 42 denture models was randomly divided into 6 groups (n = 7), with base thicknesses of 1.25, 2.50, and 3.75 mm and gypsum or silicone flask investment. Points were demarcated on the distal surface of the second molars and on the back of the gypsum cast at the alveolar ridge level to allow linear and angular measurement using AutoCAD software. The data were subjected to analysis of variance with double factor, Tukey test and Fisher (post hoc).Results: Angular analysis of the varying methods and their interactions generated a statistical difference (P = 0.023) when the magnitudes of molar inclination were compared. Tooth movement was greater for thin-based prostheses, 1.25 mm (-0.234), versus thick 3.75 mm (0.2395), with antagonistic behavior. Prosthesis investment with silicone (0.053) showed greater vertical change compared with the gypsum investment (0.032). There was a difference between the point of analysis, demonstrating that the changes were not symmetric.Conclusions: All groups evaluated showed change in the position of artificial teeth after processing. The complete denture with a thin base (1.25 mm) and silicone investment showed the worst results, whereas intermediate thickness (2.50 mm) was demonstrated to be ideal for the denture base.