A Diastereoselective Total Synthesis of trans-Trikentrin A: A Ring Contraction Approach

A new route to obtain the polyalkylated indole (+/-)-trans-trikentrin A was developed. The synthesis of this natural alkaloid features a thallium(III)mediated ring contraction reaction to obtain the trans-1,3-disubstituted five-membered ring in a diastereoselective manner. Thallium(III) is chemoselective in this rearrangement, reacting with the olefin without oxidation of the indole moiety. Other key transformations are the Bartoli`s reaction to construct the heterocyclic ring and a Heck coupling to add the carbons atom that will originate the nonaromatic cycle.

A Serious Gaming Approach For Serious Stakeholder Participation

Serious games are a category of games which are designed for a specific purpose other than for pure entertainment. It is not a new concept but serious games using real data, coupled with real time modelling and combining model results with social and economic factors opens up a new paradigm for active stakeholder participation. DHI and UNEP-DHI Centre initiated a project called Aqua Republica where a virtual world is developed which allows participants to develop a river basin and visualise the consequences of their decisions. The aim of this project is to raise awareness of the interconnectivity of water and educate on integrated water resources management. Aqua Republica combines a game layer with a water allocation model, MIKE BASIN, to create an interactive, realistic virtual environment where players play the role of a catchment manager of an undeveloped river catchment. Their main objective is to develop the river catchment to be as prosperous as it can be. To achieve that, they will need to generate a good economy in the catchment to provide the funds needed for development, have a steady food supply for their population and enough energy and water for the catchment. Through these actions by the player, a meaningful play is established to engage players and to educate them about the complex relationships between developmental actions in a river basin and the natural environment as well as their consequences. The game layer also consists of a reward system to encourage learning. People can play and replay the game, get rewarded from performing the right principles and penalised from failures in the game. This abstract will explain the concept of the game and how it has been used in a stakeholder participation environment.

Nonlinear pricing beyond the demand profile approach

Wilson [16] introduced a general methodology to deal with monopolistic pricing in situations where customers have private information on their tastes (‘types’). It is based on the demand profile of customers: For each nonlinear tariff by the monopolist the demand at a given level of product (or quality) is the measure of customers’ types whose marginal utility is at least the marginal tariff (‘price’). When the customers’ marginal utility has a natural ordering (i.e., the Spence and Mirrlees Condition), such demand profile is very easy to perform. In this paper we will present a particular model with one-dimensional type where the Spence and Mirrlees condition (SMC) fails and the demand profile approach results in a suboptimal solution for the monopolist. Moreover, we will suggest a generalization of the demand profile procedure that improves the monopolist’s profit when the SMC does not hold.

Coordenação no sistema agroindustrial da borracha natural : um estudo das relações entre produtores rurais e usinas beneficiadoras paulistas

O enfoque da Nova Economia Institucional é utilizado no estudo de sistemas agroindustriais brasileiros, mas ainda há poucos trabalhos sobre as relações entre produtores rurais e indústrias processadoras. O objetivo deste estudo é aferir o alinhamento das características das transações com os modos de governança adotados na comercialização de borracha natural entre produtores rurais e indústrias de beneficiamento primário. Busca-se confrontar os resultados com as previsões da teoria da Economia dos Custos de Transação, que prevê a adoção da governança mais eficiente, contingenciada ao ambiente transacional. Esta pesquisa utiliza um enfoque pioneiro para o setor. A primeira parte consiste na exploração qualitativa das transações entre produtores rurais e usinas beneficiadoras e na descrição dos elementos que compõe o sistema agroindustrial da borracha natural no Estado de São Paulo. Os resultados desta etapa são utilizados para refinar as hipóteses da etapa quantitativa, que relacionam os modos de governança adotados aos investimentos em ativos específicos, como o plantio de seringueiras, à frequência, à incerteza e à assistência técnica associadas à transação. Os resultados, apesar das limitações devido ao tamanho pequeno da amostra, sugerem que a quantidade de borracha comercializada influi positivamente na adoção de modos de governança mais coordenados e que a recorrência das transações provavelmente está associada a contratos relacionais. A hipótese da endogeneidade é rejeitada.

Do brazilian states engage in the fiscal war of ports? An empiric study of tax competition and an analysis of a natural experiment: the brazilian senate resolution 13/2012

O fim do ano de 2014 marcou o segundo aniversário da Resolução 13/2012 (R13) do Senado brasileiro. Grosso modo, R13 constituiu-se de um normativo do Senado cujo objetivo era o de por um fim na Guerra Fiscal dos Portos (FWP), uma competição fiscal entre os estados que se dá através da concessão de benefícios fiscais sobre operações interestaduais com mercadorias importadas de modo a atrair empresas importadoras para o território do estado concedente. R13 diminuiu o nível da tributação sobre tais operações, esperando com isso diminuir os lucros auferidos e a propensão das firmas de aceitarem tais regimes especiais de incentivação fiscal. Nada obstante, R13 gerou uma grande discussão sobre se os benefícios da atração de investimentos para um estado em particular superariam ou não os custos que esse estado incorreria em renunciar receitas tributárias em razão concessão desses benefícios fiscais. O objetivo do presente trabalho é o de dar uma contribuição a essa discussão, testando se um comportamento de interação estratégica entre estados, tal como aquele que supostamente ocorre no contexto da FWP, de fato emerge dos dados de importação coletados de janeiro de 2010 a maio de 2015, e, também, testando se a R13 de fato afetou tal comportamento de interação estratégica. Utiliza-se aqui um modelo de econometria espacial, no qual se especifica uma matriz de pesos que agrega o nível de importação das jurisdições concorrentes, organizando os dados em um painel de efeitos fixos. Os resultados sugerem que existe um comportamento de interação estratégica entre os estados e que a R13 de fato impactou tal comportamento.

Avaliação Pós-Ocupação da iluminação natural das salas dos setores de aulas teóricas da Universidade Federal do Rio Grande do Norte

The objective of this study is to assess the natural light of the classrooms sectors, at Universidade Federal do Rio Grande do Norte. It was applied the Post-Occupation Evaluation technique, by using questionnaires and brightness levels measurements inside the classrooms. In order to check the users satisfaction degree, it was initially done a general approach on the related aspects to natural light: their characteristics, availability, sources, opening systems and evaluating tools. It was also determined the necessary brightness levels for the activities development in the classroom and the Post-Occupation Evaluation technique used in the search analyses. Then, it was made the UFRN Campus` characterization; the models` definition which formed the data collection basis; the detailing of the procedures used in the research, the processing description and the data analysis. Subsequently, the results that clarify the issues raised were shown through quantitative and / or qualitative data analyses. This research notes a high level of satisfaction by the users, despite some problems such as the reflections occurrence on the board, the lack of uniformity and, occasionally, the brightness low levels

Development of a new analytical approach based on cellulose membrane and chelator for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed in this study, based on a system equipped with a cellulose membrane and a tetraethylenepentamine hexaacetate chelator (MD-TEPHA) for in situ characterization of the lability of metal species in aquatic systems. To this end, the DM-TEPHA system was prepared by adding TEPHA chelator to cellulose bags pre-purified with 1.0 mol L-1 of HCl and NaOH solutions. After the MD-TEPHA system was sealed, it was examined in the laboratory to evaluate the influence of complexation time (0-24 h), pH (3.0, 4.0, 5.0, 6.0 and 7.0), metal ions (Cu, Cd, Fe, Mn and Ni) and concentration of organic matter (15, 30 and 60 mg L-1) on the relative lability of metal species by TEPHA chelator. The results showed that Fe and Cu metals were complexed more slowly by TEPHA chelator in the MD-TEPHA system than were Cd, Ni and Mn in all pH used. It was also found that the pH strongly influences the process of metal complexation by the MD-TEPHA system. At all the pH levels, Cd, Mn and Ni showed greater complexation with TEPHA chelator (recovery of about 95-75%) than did Cu and Fe metals. Time also affects the lability of metal species complexed by aquatic humic substances (AHS); while Cd, Ni and Mn showed a faster kinetics, reaching equilibrium after about 100 min, and Cu and Fe approached equilibrium after 400 min. Increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS-metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems. (c) 2006 Elsevier B.V. All rights reserved.

A non-invasive method for silencing gene transcription in honeybees maintained under natural conditions

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

Correlato hormonal do comportamento reprodutivo de machos de sagüi comum (Callithrix jacchus) em ambiente natural

Contrary to what is recorded for Callithrix jacchus females, the social interactions and hormonal profiles of males are less studied, and mainly in wild groups. The goal of this study was to investigate the behavioral and endocrine profiles of reproductive (RMs) and non-reproductive (NRs) common marmoset adult free-ranging males living in two natural groups (GC1 and GR2). The groups inhabited the area of the Escola Agrícola de Jundiaí/UFRN, located in Macaíba, Brazil. Fecal collection for cortisol and androgen measurement and behavioral monitoring was carried out during the active phase from April to September, 2005. For behavioral data collection the focal instantaneous method was used every 5 min, for a total of 11.563 records. Statistical analysis was performed using non parametric tests and p < 0.05. Besides showing diurnal variation, the frequency of affiliative behaviors was significantly higher for RMs toward reproductive females than for NRs. Affiliative interactions of RMs with both reproductive females and NRs were similar, probably related to pair bond formation and helper recruitment, respectively. Parental care was also similar for both RMs and NRs. Both androgen and cortisol levels increased after the birth of the infants, mainly in RMs. The longitudinal profile of androgens fluctuates more in response to agonistic encounters and sexual behavior than that of cortisol. The mean basal excretion of both hormones was significantly higher in RMs and seems to reflect their higher participation in territorial vigilance and mate guarding behaviors. Significant positive correlations were found between agonism and cortisol and androgen hormones. These results describe, for the first time, the behavioral and hormonal profiles of common marmosets living in free-ranging groups and suggest that reproductive males are more responsive both behaviorally and hormonally to social group dynamics

Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids

This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M-AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd (II), and Zn(II) were carried out to characterize the stability of the metal-AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, São Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal-natural organic matter (M-NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations > 485 mu g L(-1) were necessary to obtain maximum exchange of the complexes Mn-NOM and Fe-NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments.

A comparative study of the non-isothermal degradation of natural rubber from Mangabeira (Hancornia speciosa Gomes) and Seringueira (Hevea brasiliensis)

Due to the increasing search for alternative sources of natural rubber (NR) whose properties are similar to Hevea brasiliesis, several sources have been studied in the past few years. Among them, Mangabeira (Hancornia speciosa Gomes), which is native to Amazon rainforest and other regions of Brazil, has a potential as another viable rubber source. As a continuation of a series of comparative studies between Hancornia and Hevea (clone RRIM 600) these two species by our research team, their thermal behavior was analyzed by thermogravimetry (TG) using Flynn-Wall-Ozawa's approach in order to obtain kinetic parameters (reaction order, pre-exponential factor and activation energy) of the decomposition process. Results indicated that the thermal behavior of NR from Hancornia was comparable to Hevea with some differences observed as follows: reaction order for Hancornia was higher than for Hevea at the beginning of degradation and very close for temperatures over 350 A degrees C; activation energy and pre-exponential factor had the same trend, i.e., increased with increasing degree of conversion remaining almost constant between 20 and 70% and then increasing for higher degrees, although Hevea was slightly more thermally stable than Hancornia. These major influences in the degradation process in the early stage are attributed to differences in non-rubber constituents present in these two species.

Effect of water storage on the shear strength and fatigue limit of the reline resin bond to denture base resins

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

INFLUENCE of DIFFERENT SURFACE CONDITIONING PROTOCOLS on MICROTENSILE BOND STRENGTH of SELF-ADHESIVE RESIN CEMENTS TO DENTIN

Statement of problem. According to manufacturers, bonding with self-adhesive resin cements can be achieved without any pretreatment steps such as etching, priming, or bonding. However, the benefit of saving time with these simplified luting systems may be realized at the expense of compromising the bonding capacity.Purpose. The purpose of this study was to assess whether different dentin conditioning protocols influence the bond performance of self-adhesive resin cements to dentin.Material and methods. Flat dentin surfaces from 48 human molars were divided into 4 groups (n=12): 1) control, no conditioning; 2) H(3)PO(4), etching with 37% H(3)PO(4) for 15 seconds; 3) SEBond, bonding with self-etching primer adhesive (Clearfil SE Bond); and 4) EDTA, etching with 0.1M EDTA for 60 seconds. The specimens from each dentin pre-treatment were bonded using the self-adhesive cements RelyX Unicem, Maxcem or Multilink Sprint (n=4). The resin-cement-dentin specimens were stored in water at 37 degrees C for 7 days, and serially sectioned to produce beam specimens of 1.0 mm(2) cross-sectional area. Microtensile bond strength (mu TBS) testing was performed at 1.0 mm/min. Data (MPa) were analyzed by 2-way ANOVA and Tukey multiple comparisons test (alpha=.05). Fractured specimens were examined with a stereomicroscope (x40) and classified as adhesive, mixed, or cohesive. Additional bonded interfaces were evaluated under a scanning electron microscope (SEM).Results. Cement-dentin mu TBS was affected by the dentin conditioning approach (P <.001). RelyX Unicem attained statistically similar bond strengths to all pre-treated dentin surfaces. H(3)PO(4)-etching prior to the application of Maxcem resulted in bond strength values that were significantly higher than the other groups. The lowest mu TBS were attained when luting Multilink Sprint per manufacturers' recommendations, while H(3)PO(4)-etching produced the highest values followed by Clearfil SE bonding and EDTA. SEM observations disclosed an enhanced potential of the self-adhesive cements to form a hybrid layer when applied following manufacturer's instructions.Conclusions. When evaluated self-adhesive resin cements are used, selectively etching dentin with H(3)PO(4) prior to luting results in the most effective bonding. (J Prosthet Dent 2011;105:227-235)

Duffin-Kemmer-Petiau theory in the causal approach

In this paper we consider the scalar sector of Duffin-Kemmer-Petiau theory in the framework of Epstein-Glaser causal method. We calculate the lowest order distributions for Compton scattering, vacuum polarization, self-energy and vertex corrections. By requiring gauge invariance of the theory we recover, in a natural way, the scalar propagator of the usual effective theory.

NONLEPTONIC ANNIHILATION DECAYS of B MESON WITH A NATURAL INFRARED CUTOFF

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)