Sequential IRMPD of XGe(OEt)(4)(-) ions: Gas-phase synthesis of novel oxy-germanium anions

The gas-phase ion/molecule reactions of F(-) and EtO(-) with Ge(OEt)(4) yield readily and exclusively pentacoordinated complexes XGe(OEt)(4)(-) (X = F, EtO) at pressures in the 10(-8) T range as observed by FT-ICR techniques. These hypervalent species are prone to undergo sequential fragmentations induced by infrared multiphoton excitation that lead to a variety of germyl and germanate anions. In the case of FGe(OEt)(4)(-), three primary competitive channels are observed in the IRMPD process that can be identified as (EtO)(3)GeO(-), F(EtO)(2)GeO(-) and (EtO)(3)Ge(-). Ab initio calculations have been carried out to characterize the primary fragmentation paths induced by IRMPD and the most favorable structure of the resulting anions. The gas-phase acidity of a number of these germanium-containing ions have been estimated by bracketing experiments and by theoretical calculations. Germanate anions such as (EtO)(3)GeO(-) undergo some interesting reactions with H(2)S to give rise to anions such as (EtO)(3)GeS(-) and (EtO)(2)Ge(OH)S(-). (C) 2010 Elsevier B.V. All rights reserved.

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether, lithium perchlorate, and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) with LiClO(4), PEGdME/LiClO(4), and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, PEGdME/[bmim]PF(6), are compared. Raman spectroscopy suggests stronger interactions in PEGdME/LiClO(4) than PEGdmE/[bmim]PF(6), thus corroborating previous results obtained by molecular dynamics simulations. Quantum Chemistry methods have been used to calculate vibrational frequencies and the equilibrium structure of segments of the polymer chain around the cation. A consistent picture has been obtained from Raman spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulations for these polymer electrolytes. (C) 2010 Elsevier B.V. All rights reserved.

The gas-phase alcoholysis of protonated homoleptic alkoxysilanes

Tetra-alkoxysilanes are common and useful reagents in sol-gel processes and understanding their reactivity is important in the design of new materials. The mechanism of gas-phase reactions that mimic alcoholyis of Si(OMe)(4) (usually known as TMOS) under acidic conditions have been studied by Fourier transform ion cyclotron resonance techniques and density functional calculations at the B3LYP/6-311+G(d,p) level. The proton affinity of TMOS has been estimated at 836.4 kJ mol(-1) and protonation of TMOS gives rise to an ionic species that is best represented as trimethoxysilyl cations associated with a methanol molecule. Protonated TMOS undergoes rapid and sequential substitution of the methoxy groups in the gas-phase upon reaction with alcohols. The calculated energy profile of the reaction indicates that the substitution reaction through an S(N)2 type mechanism may be more favorable than frontal attack at silicon. Furthermore, the sequential substitution reactions are promoted by a mechanism that involves proton shuttle from the most favorable protonation site to the oxygen of the departing group mediated by the neutral reagent molecule.

Ab Initio Analysis of Monomers and Dimers of Trialkylphosphine Oxides: Structural and Thermodynamic Stability

Structural and thermodynamic stabilities of monomers and dimers of trialkylphosphine oxides (TRPO) were Studied using quantum chemistry calculations. Density functional theory calculations were carried Out and the structures Of four TRPO have been determined: TMPO (methyl; R = CH(3)), TEPO (ethyl; R = CH(3)CH(2)), TBPO (n-butyl; R = CH(3)(CH(2))(3)), and TOPO (n-octyl; R = CH(3)(CH(2))(7)). TRPO homodimers were investigated considering two isomeric possibilities for each dimer. Relative binding energies and the enthalpic and entropic contributions to the Gibbs free energy were Calculated for all dimers. The formation of dimers from the individual monomeric TRPO species as a function of temperature was also analyzed. (C) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 109: 250-258, 2009

The First Provenance Challenge

The first Provenance Challenge was set up in order to provide a forum for the community to understand the capabilities of different provenance systems and the expressiveness of their provenance representations. To this end, a Functional Magnetic Resonance Imaging workflow was defined, which participants had to either simulate or run in order to produce some provenance representation, from which a set of identified queries had to be implemented and executed. Sixteen teams responded to the challenge, and submitted their inputs. In this paper, we present the challenge workflow and queries, and summarise the participants contributions.

Reservoir Management For Flood And Drought Protection Using Infinite Horizon Model Predictive Control

Model Predictive Control (MPC) is a control method that solves in real time an optimal control problem over a finite horizon. The finiteness of the horizon is both the reason of MPC's success and its main limitation. In operational water resources management, MPC has been in fact successfully employed for controlling systems with a relatively short memory, such as canals, where the horizon length is not an issue. For reservoirs, which have generally a longer memory, MPC applications are presently limited to short term management only. Short term reservoir management can be effectively used to deal with fast process, such as floods, but it is not capable of looking sufficiently ahead to handle long term issues, such as drought. To overcome this limitation, we propose an Infinite Horizon MPC (IH-MPC) solution that is particularly suitable for reservoir management. We propose to structure the input signal by use of orthogonal basis functions, therefore reducing the optimization argument to a finite number of variables, and making the control problem solvable in a reasonable time. We applied this solution for the management of the Manantali Reservoir. Manantali is a yearly reservoir located in Mali, on the Senegal river, affecting water systems of Mali, Senegal, and Mauritania. The long term horizon offered by IH-MPC is necessary to deal with the strongly seasonal climate of the region.

Música em Movimento: a linguagem Motion Graphics nos videoclipes brasileiros (1990-2010)

SOUZA, Luciano. Música em movimento: a linguagem Motion Graphics nos videoclipes brasileiros (1990 -2010). 100f. Dissertação (Mestrado em Comunicação)-Universidade Municipal de São Caetano do Sul, São Caetano do Sul, 2012.

Memórias de jornalistas: narrativas de profissionais da grande imprensa sobre a eleição, o governo e o impeachment de Fernando Collor

A presente pesquisa tem por tema as vivências de jornalistas na cobertura do “período Collor”, desde a eleição presidencial em 1989 até o processo de impeachment em 1992. Origina-se do questionamento sobre quais recordações jornalistas, que, na época, atuavam em grandes órgãos de imprensa, guardam na memória acerca daquele importante período da história recente do país. Busca, com isso, resgatar a memória do período sob o ponto de vista dos jornalistas convidados a participarem deste estudo, assim como identificar experiências e vivências que possam contribuir para uma melhor compreensão do fazer jornalístico nos últimos anos do século XX. Para tanto, parte do registro de Narrativas Orais de Histórias de Vida, baseada nos métodos da História Oral, que valoriza os indivíduos e suas respectivas histórias de vida como forma de recuperar o passado aos olhos do tempo presente, por meio de lembranças narradas oralmente. A pesquisa tem como fatores de inovação a busca por uma dimensão subjetiva nos estudos científicos da Comunicação Social e as transformações comunicacionais vividas por uma geração de jornalistas, representada pela comunidade estudada. A metodologia adotada permitiu uma construção histórica do período, a partir das memórias dos entrevistados, assim como possibilitou melhor compreender o fazer jornalístico de uma geração. Conclui-se, assim, com base nas narrativas, que os acontecimentos do “período Collor” ajudam a evidenciar os complexos elementos que interferem no exercício cotidiano do jornalismo, chamando a atenção, sobretudo, para as constantes tensões provocadas pelo contraditório discurso que propaga o mito da isenção jornalística e as decisões tomadas no ato da edição; a forma como o jornalista constrói o mundo que encontra ao produzir a notícia e as escolhas subjetivas feitas ao longo da vida profissional, que os constitui como sujeitos da ação do jornalismo.