Solvatochromic Shift of the pi -> pi* Transition in All-Trans, Cis-13, Cis-11, Cis-9, and Cis-7 Retinal Isomers Induced by Water and Methanol

The solvatochromic shift of the lowest singlet it pi -> pi* electronic transition in the all-trans, cis-13, cis-11, cis-9, and cis-7 retinal isomers were computed under the influence of water, methanol, and benzene solvents. Excitation energies were calculated in gas phase and in solution. The calculations in solution were performed considering the sequential Monte Carlo (MC) /Quantum Mechanical approach. The MC simulations were performed considering the full retinal isomer molecules and 900 water molecules, 900 methanol, or 400 benzene ones. The OPLS/AA parametrization was chosen for retinal, methanol, and benzene molecules and the SPC model was used for water one. From the MC calculations 100 independent configurations were selected, with 100 solvent molecules in thermodynamical equilibrium at T = 298.15 K. Average point-charges were obtained from those independent configurations for water, methanol, and benzene solvent. TDDFT and CASSCF//CASPT2 methodologies were used to compute the vertical excitation energy of the retinal isomers in different environment. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110: 2076-2087, 2010

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), (1)H and (13)C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, (13)C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.

2-Aminopurine non-radiative decay and emission in aqueous solution: A theoretical study

The minimum energy path along the lowest-lying pi pi* excited state of 2-aminopurine was calculated to elucidate the mechanisms of radiationless decay and emission in water. The sequential Monte Carlo quantum mechanics approach with a multiconfigurational and perturbative description of the wave function was employed to compute the minimum, transition state, and conical intersection. It was found that the barrier in the potential energy surface to access the conical intersection funnel increases in aqueous environment, making the system prone to enlarge the emission yield. These results rationalize the observed enhancement of emission in 2-aminopurine upon increasing of the solvent polarity. (c) 2008 Elsevier B.V. All rights reserved.

FT-Raman investigation of biodegradable polymers: Poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

This work presents a FT-Raman study (lambda(0) = 1064 nm) of naturally occurring polyester poly[(R)-3-hydroxybutyrate] (PHB) and its copolymer poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate] (PHBV) with 5,8 and 12 mol % of HV (hydroxyvalerate). The FT-Raman spectra of films indicate that full width at half height of the band centered at 1725 cm(-1) and relative intensity of bands at 1443 and 1458 cm(-1) can be use to estimate the crystalline degree in film samples. The similarity between Raman spectra of molten PHB and PHBV and theirs CDCl(3) solutions suggested that molten polymers present similar conformation than polymers in solution. Raman data of these samples showed that bands at 1220, 1402, 1725, 2998 and 3009 cm(-1) are due to crystalline helical structure and the bands at 1453, 1740, 2881, 2938 and 2990 cm(-1) are originated from disordered domains. It is shown that composition of PHBV samples can be estimated by analyzing the ratio of the intensity of the bands at 2938 cm(-1) (nu C-H) and 1740 cm(-1) (nu C=O) in the spectra of solutions and of bands at 1354 (wCH(2)) and 1740 cm(-1) (nu C=O) in spectra of molten polymers. (C) 2010 Elsevier B.V. All rights reserved.

Temperature (over) compensation in an oscillatory surface reaction

Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. We study the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 degrees C, and the oscillations are studied under galvanostatic control. Under oscillatory conditions, only non-Arrhenius behavior is observed. Overcompensation with temperature coefficient (q(10), defined as the ratio between the rate constants at temperature T + 10 degrees C and at T) < I is found in most cases, except that temperature compensation with q(10) approximate to I predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, nonoscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than, from a weak temperature dependence of the individual steps.

Soda-Treated Sisal/Polypropylene Composites

Treated sisal fibers were used as reinforcement of polypropylene (PP) composites, with maleic anhydride-grafted PP (MAPP) as coupling agent. The composites were made by melting processing of PP with the fiber in a heated roller followed by multiple extrusions in a single-screw extruder. Injection molded specimens were produced for the characterization of the material. In order to improve the adhesion between fiber and matrix and to eliminate odorous substances, sisal fibers were treated with boiling water and with NaOH solutions at 3 and 10 wt.%. The mechanical properties of the composites were assessed by tensile, bend and impact tests. Additionally, the morphology of the composites and the adhesion at he fiber-matrix interface were analyzed by SEM. The fiber treatment led to very light and odorless materials, with yields of 95, 74 and 62 wt.% for treatments with hot water, 3 and 10 wt.% soda solution respectively. Fiber treatment caused an appreciable change in fiber characteristics, yet the mechanical properties under tensile and flexural tests were not influenced by that treatment. Only the impact strength increased in the composites with alkali-treated sisal fibers.

Genetic heterogeneity of within-family variance of body weight in Atlantic salmon (Salmo salar)

BACKGROUND: Canalization is defined as the stability of a genotype against minor variations in both environment and genetics. Genetic variation in degree of canalization causes heterogeneity of within-family variance. The aims of this study are twofold: (1) quantify genetic heterogeneity of (within-family) residual variance in Atlantic salmon and (2) test whether the observed heterogeneity of (within-family) residual variance can be explained by simple scaling effects. RESULTS: Analysis of body weight in Atlantic salmon using a double hierarchical generalized linear model (DHGLM) revealed substantial heterogeneity of within-family variance. The 95% prediction interval for within-family variance ranged from ~0.4 to 1.2 kg2, implying that the within-family variance of the most extreme high families is expected to be approximately three times larger than the extreme low families. For cross-sectional data, DHGLM with an animal mean sub-model resulted in severe bias, while a corresponding sire-dam model was appropriate. Heterogeneity of variance was not sensitive to Box-Cox transformations of phenotypes, which implies that heterogeneity of variance exists beyond what would be expected from simple scaling effects. CONCLUSIONS: Substantial heterogeneity of within-family variance was found for body weight in Atlantic salmon. A tendency towards higher variance with higher means (scaling effects) was observed, but heterogeneity of within-family variance existed beyond what could be explained by simple scaling effects. For cross-sectional data, using the animal mean sub-model in the DHGLM resulted in biased estimates of variance components, which differed substantially both from a standard linear mean animal model and a sire-dam DHGLM model. Although genetic differences in canalization were observed, selection for increased canalization is difficult, because there is limited individual information for the variance sub-model, especially when based on cross-sectional data. Furthermore, potential macro-environmental changes (diet, climatic region, etc.) may make genetic heterogeneity of variance a less stable trait over time and space.

Distribution strategies for the base of the pyramid: an exploratory study in Brazil

Access has been one of the main difficulties companies have faced in emerging markets (PRAHALAD, 2005). The capillarity of the market, the existence of small, not professionalized and sometimes informal retailers, the lack of infrastructure and high transportation costs are some of the distribution challenges companies face in poorer regions. The literature concerning the Base of the Pyramid (BoP) is still recent and only after the seminal article by Prahalad and Hart (2002), it evolved into many different management perspectives. However, there is a lack of researches concerning distribution strategies to the BoP. Therefore, the main objective of this research is to identify, in the perception of executives working in the market, the conditions associated to a satisfactory distribution for the BoP market in Brazil and to build a substantive theory that helps to shed light to the understanding of the distribution phenomenon adopted by consumer goods companies to reach the BoP market in Brazil. In order to accomplish the objectives of this thesis, a grounded theory methodology (Glaser; Strauss, 1967; Corbin; Strauss, 2008) was used. This approach helped to identify the channel strategies used by local and global companies in the market. Many techniques for data collection were applied. The most important one was in-depth interviews with 26 executives from 24 different consumer goods companies in Brazil. Among the companies there were small, medium and large enterprises; which were also grouped as manufacturers, distributors and retailers. Furthermore, secondary data were examined to identify business strategies to reach BoP and map global distribution initiatives. A database from a consumer panel was also used to analyze what and where BoP consumers purchase non-durable goods. It was verified that small and traditional retailing is a very strong format in BoP markets and in the Northern/Northeastern regions. Cash & Carry is a format that is growing a lot. On the other hand, hypermarkets are not very used by low income population. The results suggest that three major categories are associated to a satisfactory distribution: (a) willingness, which means the effort, knowledge and enthusiasm a firm has to operate at BoP markets; (b) well-done execution, which is related to designing correctly the marketing channel and operating efficiently in an environment full of obstacles, such as lack of infrastructure, capillarity, lack of safety, regional differences and informality, and (c) relationship, which was perceived to be friendlier and essential at BoP markets, since it is very difficult for manufacturers to reach the entire market alone. It is more likely to have a satisfactory distribution when manufacturers establish strong relationships in the marketing channel. Besides, small retailers have a perception of isolation and expect a higher level of relationship. These major categories explain also the competitive advantage that local companies have in relation to MNCs and large companies. Despite of the limitations of an exploratory study, it is expected that this thesis will contribute to the BoP knowledge as well as to the identification of the peculiarities of distribution in BoP markets.

Informal wages in an economy with active labor courts

In most developing countries, job regulations and the justice branch interfere on several aspects of labor contracts. Inspired by this fact, we build a model that explores the role of labor courts in the determination of the di¤erence between formal and informal wages. We show that the presence of active labor courts in an environment where labor relations are subject to asymmetries of information reproduces features documented by the empirical literature. The main implications of our model are tested using Brazilian data.

Performance of incentive contracts in highway PPP projects in Brazil

Private-Public Partnerships (P.P.P.) is a new contractual model institutionalized in 2004 that could be used to remedy to the infrastructure deficit in Brazil. In a context of a principal and agent relation, the public partner goal is to give incentives to the private partner in the contract so that their interests are aligned. This qualitative research presents the findings of an empirical study examining the performance of incentive PPP contracts in Brazil in the highway sector. The goal is to explain how the contracting parties can align their interests in an environment of asymmetric information. Literature identified the factors that can influence PPP design and efficient incentive contracts. The study assesses the contribution of these factors in the building of PPP contracts by focusing on the case of the first and only PPP signed in the highway sector in Brazil which is the MG-050. The first step is to describe the condition of the highway network and the level of compliance of the private partner with the contract PPP MG-050. The second step is to explain the performance of the private partner and conclude if the interests of both partners were aligned in contractual aspects. On the basis of these findings and the analysis of the contract, the study formulates suggestions to improve the draft of PPP contracts from the perspective of the incentive theory of contracts.

Análise do custo-aluno das creches municipais diretas do município de Santo André

O presente estudo tem como foco o levantamento e análise do custo-aluno das creches, primeira etapa da Educação Infantil, que compreende as crianças de 0 a 3 anos de idade. Ele responde à situação problema apresentada pela Secretaria de Educação do Município de Santo André (SP), caracterizada pela necessidade do aprimoramento da gestão dos recursos financeiros em um cenário de dificuldades orçamentárias e aumento de demanda. Foram selecionadas 12 unidades municipais da rede direta, com atendimento exclusivo a crianças nesta faixa etária. A metodologia utilizada teve como base a utilização do Sistema de Informações do Orçamento Público municipal, a partir do qual foram realizadas as consultas e definições dos componentes do custo do objeto em estudo, sendo que a metodologia de acumulação de custos utilizada foi o custeio por absorção. Adicionalmente, os autores analisaram os processos administrativos relacionados aos itens de custeio e realizaram entrevistas com os diversos atores envolvidos nos processos de gestão daquela e de outras secretarias, bem como acadêmicos dedicados ao estudo de custos no setor público, cujas experiências relatadas subsidiaram a pesquisa e as avaliações realizadas. O estudo apontou um custo-aluno médio de R$ 11.970,72 sendo que, para melhor análise dos resultados, as unidades escolares foram agrupadas em três categorias de acordo com o número de alunos: i) pequeno porte: com até 149 alunos (três unidades); ii) médio porte: entre 150 e 190 alunos (cinco unidades); e, iii) grande porte: com mais de 190 alunos (quatro unidades). A partir dessa divisão foi possível concluir que as creches de grande porte apresentaram vantagem comparativa em relação às demais, com custo-aluno médio de R$ 11.684,03, seguidas das creches de médio porte, R$ 11.751,46 e pelas unidades de pequeno porte, que apresentaram o custo-aluno de R$ 13.235,88, ou seja, 13,23% acima das escolas de grande porte. Esses resultados indicam a existência de ganhos de escalas de acordo com o porte da creche e pode subsidiar a tomada de decisão dos gestores para futuros projetos de expansão da rede pública de creches.

Coordination in brazilian pharmaceutical supply chains

Supply chain coordination (SCC) can be a challenge for many organizations as different firms in the same chain has different expectations and interdependencies (Arshinder & Deshmukh, 2008). Lack of SCC can result in the bullwhip effect and poor performance for a firm and its partners. By investigating the phenomenon in the Brazilian pharmaceutical supply chain using a qualitative research, this paper aims to understand the main issues that avoid a better integrated chain. Results of 21 interviews suggested that the lack of coordination in this environment was influenced by the network design and the history of the sector in Brazil, as well as scarce resources

Exploring the dimensions of eco-feedback in the wild

Worldwide reports about energy usage have noted the importance of the domestic energy consumption sector in the worldwide scenario. This fact motivated and supported the birth and spread of the so-called eco-feedback devices. Such devices provide information about individual or group energy consumption behavior with the goal of reducing the impact in the environment. Motivated by the body of work which questions the long term effectiveness of eco-feedback systems, this thesis focus on evaluating in-the-wild the long term usage of eco-feedback systems. We have conducted five long term studies with different eco-feedback systems designed to evaluate different dimensions in the design of eco-feedback plus two more focused short term studies aimed at studying concrete approaches. Our summary reports on the fact that the there is a novelty effect associated with ecofeedback systems in which the usage of these devices declines significantly after a month. We did not found evidence that the novelty effect is related to location or the type of information represented, nor that the decrease in the eco-feedback usage could lead to the consumption relapsing to values previous to the introduction of the eco-feedback. Our work has also generated other contributions related to the positioning of the feedback, using metaphors for representing the consumption and presenting information about the source of the energy in the feedback.

Information literacy: uma análise nas bibliotecas escolares da rede privada em Natal / RN

GUEDES, Clediane de Araújo; FARIAS, Gabriela Belmont de. Information literacy: uma análise nas bibliotecas escolares da rede privada em Natal / RN. Revista Digital de Biblioteconomia e Ciência da Informação, Campinas, v. 4, n. 2, p. 110-133, jan./jun. 2007