Electronic Structure and Chemical Bonding in the Ground and Low-Lying Electronic States of Ta(2)

The electronic structure and chemical bonding of the ground and low-lying Lambda - S and Omega states of Ta(2) were investigated at the multiconfiguration second-order perturbation theory (CASSCF//CASPT2) level. The ground state of Ta(2) is computed to be a X(3)Sigma(-)(g) state (R(e) = 2.120 angstrom, omega(e) = 323 cm(-1), and D(e) = 4.65 eV), with two low-lying singlet states close to it (a(1) Sigma(+)(g) : T(e) = 409 cm(-1), R(e) = 2.131 angstrom, and omega(e) = 313 cm(-1); b(1) Gamma(g): T(e) = 1, 038 cm(-1), R(e) = 2.127 angstrom, and omega(e) = 316 cm(-1)). These electronic states are derived from the same electronic configuration: vertical bar 13 sigma(2)(g)14 sigma(2)(g)7 delta(2)(g)13 pi(4)(u)>. The effective bond order of the X(3) Sigma(-)(g) state is 4.52, which indicates that the Ta atoms are bound by a quintuple chemical bond. The a(1) Sigma(+)(g) state interacts strongly with the X(3)Sigma(-)(g) g ground state by a second-order spin-orbit interaction, giving rise to the (1)0(g)(+) (ground state) (dominated by the X(3)Sigma(-)(g) Lambda - S ground state) and (9)0(g)(+) (dominated by the a(1) Sigma(+)(g) Lambda - S state) Omega states. These results are in line with those reported for the group 5B homonuclear transition metal diatomics. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1306-1315, 2011

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.

Ion pair stabilization effects on a series of procaine structural analogs

In this work, a series of 10 structural procaine analogs have been synthesized in order to investigate the structural features affecting the stability of ion pair formation and its influence on the lipophilicity of ionizable compounds. The structural variation within this series was focused on the terminal nitrogen substituents and on the intermediate chain linkage nature. The hydrophobic parameters log P(n) and log P(i) (partition coefficient of the neutral and ionic species, respectively), as well as the ionization constants pK(a) and pK(a)(oct), were obtained from log D-pH profiles measured at pH values ranging from 2 to 12. The difference between log P(i) and log P(n) values (i.e. difflog P) of each prepared compound was considered a measure of the stability of ion pair formation. In this set, the difflog P values varied nearly over one log unit, ranging from -2.40 to -3.37. It has been observed that the presence of hydrogen bonding groups (especially donor) and low steric hindrance around the terminal amine ionizable group increases the relative lipophilicity of the ionic species as compared to the corresponding neutral species. These results were interpreted as due to the increased stability of ion pairs of the compounds bearing these structural features. (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.

Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for (lie ionization of the compounds. [it our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed: these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second P-O-phenol bonds, eventually leading to the formation of phenol, Phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different Structure and the products detected suggest scission of either the P-O-hydrocarbon or one of the P-O-phenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products. (C) 2008 Elsevier B.V. All rights reserved.

Dereplication of Bromotyrosine-derived Metabolites by LC-PDA-MS and Analysis of the Chemical Profile of 14 Aplysina Sponge Specimens from the Brazilian Coastline

In order to investigate the chemical profile of 14 specimens of Aplysina spp. marine sponges, we have developed a method based on LC-PDA-MS for the detection of bromotyrosine-derived metabolites. The method enabled the dereplication of three distinct chemotypes of bromotyrosine-derived compounds based on UV absorptions, which were further refined by electrospray ionization-mass spectrometry analysis of the brominated quasi-molecular ion clusters. This procedure led to either a single compound assignment, or a maximum of two possible isobaric compounds. The dereplication study indicated that the chemical profile of the 14 specimens of Aplysina spp. analyzed presented practically the same dibromotyrosine-derived compounds. The results obtained suggested a possible biogenetic pathway for the formation of dibromotyrosine-derived compounds of wide occurrence in Verongida sponges.

A combined X-ray and theoretical study of flavonoid compounds with anti-inflammatory activity

The structure of 7,4`-dimethoxy-3`-acetylflavone (tithonin-Ac) has been determined by X-ray diffraction and its geometry is compared with optimized geometrical parameters obtained by means of density functional theory at the B3LYP/6-311++G(d,p) level of calculation. in addition, vertical ionization potential (IPv) and acidity for tithonin-Ac and two derivatives have been also calculated. Calculations of spin densities were also performed for the radical formed by the electron abstraction of other flavones. The unpaired electron is located on C3 carbon atom (21-25%). (C) 2008 Elsevier B.V. All rights reserved.

A theoretical study on the XeF(2) molecule

A relativistic four-component study was performed for the XeF(2) molecule by using the Dirac-Coulomb (DC) Hamiltonian and the relativistic adapted Gaussian basis sets (RAGBSs). The comparison of bond lengths obtained showed that relativistic effects on this property are small (increase of only 0.01 angstrom) while the contribution of electron correlation, obtained at CCSD(T) or CCSD-T levels, is more important (increase of 0.05 angstrom). Electron correlation is also dominant over relativistic effects for dissociation energies. Moreover, the correlation-relativity interaction is shown to be negligible for these properties. The electron affinity, the first ionization potential and the double ionization potential are obtained by means of the Fock-space coupled cluster (FSCC) method, resulting in DC-CCSD-T values of 0.3 eV, 12.5 eV and 32.3 eV, respectively. Vibrational frequencies and some anharmonicity constants were also calculated under the four-component formalism by means of standard perturbation equations. All these molecular properties are, in general, ill satisfactory agreement with available experimental results. Finally, a partition in terms of charge-charge flux-dipole flux (CCFDF) contributions derived by means of the quantum theory of atoms in molecules (QTAIM) in non-relativistic QCISD(FC)/3-21G* calculations was carried out for XeF(2) and KrF(2). This analysis showed that the most remarkable difference between both molecules lies on the charge flux contribution to the asymmetric stretching mode, which is negligible in KrF(2) but important in XeF(2). (c) 2008 Elsevier B.V. All rights reserved.

Simultaneous analysis of five antidepressant drugs using direct injection of biofluids in a capillary restricted-access media-liquid chromatography-tandem mass spectrometry system

Direct analysis, with minimal sample pretreatment, of antidepressant drugs, fluoxetine, imipramine, desipramine, amitriptyline, and nortriptyline in biofluids was developed with a total run time of 8 min. The setup consists of two HPLC pumps, injection valve, capillary RAM-ADS-C18 pre-column and a capillary analytical C 18 column connected by means of a six-port valve in backflush mode. Detection was performed with ESI-MS/MS and only 1 mu m of sample was injected. Validation was adequately carried out using FLU-d(5) as internal standard. Calibration curves were constructed under a linear range of 1-250 ng mL(-1) in plasma, being the limit of quantification (LOQ), determined as 1 ng mL(-1), for all the analytes. With the described approach it was possible to reach a quantified mass sensitivity of 0.3 pg for each analyte (equivalent to 1.1-1.3 fmol), translating to a lower sample consumption (in the order of 103 less sample than using conventional methods). (C) 2008 Elsevier B.V. All rights reserved.

Characterization of protein hydrolysates of cosmetic use by CE-MS

Protein hydrolysates have been used as active principles in cosmetic products conferring different properties to the final formulations, which are mostly controlled by the peptide size and its amino acid sequence. In this work, capillary electrophoresis coupled to mass spectrometry analyses were carried out in order to investigate such characteristics of protein hydrolysates. Samples of different origins (milk, soy and rice) were obtained from a local company, and were analyzed without a previous preparation step. The background electrolyte (BGE) and sheath liquid compositions were optimized for each sample. The best BGE composition (860 mmol/L formic acid - pH 1.8 - in 70: 30 v/v water/methanol hydro-organic solvent) was chosen based on the overall peak resolution whereas the best sheath liquid was selected based on increased sensitivity and presented different compositions to each sample (10.9-217 mmol/L formic acid in 75: 25-25: 75 v/v water/methanol hydro-organic solvent). Most of the putative peptides in the hydrolysate samples under investigation presented molecular masses of 1000 Da or less. De novo sequencing was carried out for some of the analytes, revealing the hydrophobicity/polarity of the peptides. Hence, the technique has proved to be an advantageous tool for the quality control of industrial protein hydrolysates.

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.

An Injection-locked Diode Laser for Cold Rydberg Atom Experiments

A free-running, temperature stabilized diode laser has been injection-locked to an external cavity diode laser for use in cold Rydberg atom experiments. Cold rubidium atoms in a magneto-optical trap (MOT) are excited to Rydberg states using a 10 ns laser pulse. The Rydberg atoms spontaneously ionize due to dipole forces, and the collisional ionization dynamics are observed as a function of atom density and principal quantum number of the Rydberg state, n. The injection-locked diode laser will be used as a repumper in conjunction with a dark spontaneous-force optical trap (SPOT) to increase the Rydberg state density. We report on the design of the injection-locked laser system.

O contínuo e a região estendida de linhas estreitas das galáxias ativas ESO 362-G18 e ESO 362-G8

Foram analisados espectros óticos de fenda longa das galáxias Seyfert 1 ESO362-G18 e Seyfert 2 ESO362-G8. Estas duas galáxias apresentam emissão por gás de alta excitação em forma anisotrópica, possivelmente devido a colimação por um tóro de poeira. O objetivo do presente trabalho consiste em estudar o contínuo e a região estendida de linhas de emissão (ENLR) destes objetos. Este trabalho constitui-se no primeiro estudo detalhado realizado sobre estas galáxias. A população estelar em cada galáxia e caracterizada em função da distância ao núcleo. O contínuo nuclear e estudado em termos de duas componentes: a população estelar e a componente AGN (\Active Galatic Nuclei"). Observa-se a presença desta componente AGN na gal axia Seyfert 1 ESO362-G18. A galáxia Seyfert 2 não permite observar esta componente AGN mesmo depois de subtraída a componente de população estelar. Nas duas galáxias observa-se importante contribuição de população de idade intermediária ( 5 108 anos). A partir das linhas estreitas de emissão, mapeamos a excitação do gás interestelar ao longo da ENLR. As razões entre estas linhas de emissão são reproduzidas a partir de um modelo de fotoionização de duas componentes - uma componente limitada por matéria ("matter-bounded") e uma componente limitada por ionização ("ionization-bounded"). Este modelo, construído utilizando o código de fotoionização MAPPINGS Ic, se propõe a resolver os problemas apresentados pelos modelos tradicionais de uma componente apenas. A partir dos resultados obtidos com o modelo de duas componentes, determinamos o fator de preenchimento e o fator de cobertura do gás em função da distância ao núcleo. Utilizamos estes parâmetros para testar a consistência do modelo proposto. Por fim realizase o cálculo de balanço de fótons e estuda-se a natureza do contínuo infravermelho (IR) médio e distante - comparando-se a luminosidade observada no IR, calculada a partir dos fluxos IRAS, com a luminosidade predita para um tóro que envolve a fonte modelada e re-emite a radiação incidente no infravermelho.

Hierarquia, igualdade e diferença : lutas por reconhecimento no sul do Brasil

Este estudo busca investigar as lógicas da ação em cooperativas de produção e associações de catadores de lixo no bojo de processos de reestruturação econômica que não somente precarizam as condições de emprego, mas também implicam em processos de desassalariamento da força de trabalho. Tomando como perspectiva analítica a sociologia da experiência de François Dubet, decompomos as lógicas da ação de trabalhadores com inserção social distinta, ou seja, um primeiro grupo caracterizado por uma cultura operária e sindical e um segundo grupo caracterizado por um processo de dissociação em relação ao mundo do trabalho formal. Neste sentido, procurou-se investigar: a) as formas de inserção e integração sociais configuradas pelas relações de solidariedade, b) a dimensão da racionalidade estratégica de cada grupo traduzida nas lutas por reconhecimento, e, c) os processos de subjetivação expressos na afirmação identitária de cada coletivo de trabalhadores. Ou seja, quais as condições de possibilidade da ruptura com as hierarquias que organizam e estruturam o universo de coletivos de trabalhadores com origens sociais tão diversas quando confrontados com o princípio meta-social da igualdade? Noutras palavras, quando compelidos com a necessidade de organizar uma cooperativa ou associação, enquanto alternativa palpável de subsistência, os trabalhadores se deparam com um contexto bem diverso da situação de assalariamento. Com efeito, a experiência associativa irá implicar que a adesão à cooperativa ou associação deve ser livre e voluntária e que a gestão e os processos de deliberação devem ser democráticos. A partir da pesquisa de campo verificou-se um processo de subjetivação marcado por estratégias distintas nas cooperativas e associações: enquanto nas cooperativas a adesão dos trabalhadores era caracterizada por uma certa ambivalência entre o compromisso com o projeto de construção da cooperativa e uma postura pautada por um certo pragmatismo tipificado por um campo de possíveis restrito no tocante as alternativas de inserção social, nas associações de catadores de lixo verificou-se um processo de ruptura com os padrões de sociabilidade primária acentuadamente hierarquizados a partir da participação das mulheres nas associações, bem como um efetivo compromisso com o projeto associativo. Na esfera da ação coletiva, a constituição de cooperativas a partir de empresas em situação falimentar revelou uma nova estratégia sindical marcada por uma ação defensiva ante os processos de reestruturação econômica que eliminam postos de trabalho. Já, na ação coletiva das associações constatou-se um movimento de luta pelo reconhecimento de direitos e recuperação da cidadania. Tal movimento é caracterizado por uma lógica do respeito possuindo uma dupla inflexão, ou seja, por um lado busca romper no âmbito da esfera privada com a dominação masculina expressa num código de honra, cuja conseqüência mais dramática se traduz na violência doméstica, e por outro lado se constata um movimento em direção à esfera pública a partir da articulação de uma associação com um movimento social traduzindo desta maneira a reivindicação pelo reconhecimento da dignidade de indivíduos sujeitos a todo tipo de reconhecimento recusado.

Cidadania vis-a-vis democracia : estudo analitico-interpretativo das greves, nos anos 80, como fenomeno indicador de mudanças nas relações do trabalho em instituições universitarias da administração publica federal : UFRJ e UFF

Consiste essa dissertação num estudo analítico interpretativo indicador de das greves nos anos 80, como fenômeno indicador de mudanças nas relações do trabalho em instituições univer5it'rias da administração pública federal: UFRJ e UFF. A investigação sobre o incremento do sindicalismo de classe média, no setor público, nos anos 80 processou-se de modo a que se compreendesse/interpretasse o novo paradigma de ação sindical indicativo de mudanças no papel sócio político de atores coletivos/individuais, vis-à-vis à prática do associativismo em IFES. A opção metodológica assumida foi a de uma abordagem qualitativa do tema, utilizando-se como categorias de análise: cidadania, democracia, participação e poder, aplicadas ao estudo, numa visão comparativa dos movimentos organizados/grevistas, na UFRJ e UFF. Pelo estudo, conclui-se, em síntese, que docentes e servidores técnico-administrativos da UFRJ e UFF, via participação organizada nos movimentos grevistas dos anos 80, vieram a assumir novos papéis sociais e posições políticas, construindo ocasionando uma nova cidadania e, consequentemente, trabalho entre categorias profissionais do setor público E o federal. governo Isto, porque, graças ao seu poder de convocação/influência e pela sua seu vida associativa constituiram-se essas categorias profissionais em forças sociais/políticas suscetíveis de modificar/intervir em decisões político-administrativas que disseram respeito a formulação/gestão de políticas, com destaque para as de Pessoal das IFES e de Rendas/Salários, bem como as de Ensino Superior e de Financiamento da Educação.