Monte Carlo field-theoretic simulations for melts of symmetric diblock copolymer

Monte Carlo field-theoretic simulations (MCFTS) are performed on melts of symmetric diblock copolymer for invariant polymerization indexes extending down to experimentally relevant values of N̅ ∼ 10^4. The simulations are performed with a fluctuating composition field, W_−(r), and a pressure field, W_+(r), that follows the saddle-point approximation. Our study focuses on the disordered-state structure function, S(k), and the order−disorder transition (ODT). Although shortwavelength fluctuations cause an ultraviolet (UV) divergence in three dimensions, this is readily compensated for with the use of an effective Flory−Huggins interaction parameter, χ_e. The resulting S(k) matches the predictions of renormalized one-loop (ROL) calculations over the full range of χ_eN and N̅ examined in our study, and agrees well with Fredrickson−Helfand (F−H) theory near the ODT. Consistent with the F−H theory, the ODT is discontinuous for finite N̅ and the shift in (χ_eN)_ODT follows the predicted N̅^−1/3 scaling over our range of N̅.

Melting Regime of the Anionic Phospholipid DMPG: New Lamellar Phase and Porous Bilayer Model

Aqueous dispersions of the anionic phospholipid dimyristoyl phosphatidylglycerol (DMPG) at pH above the apparent pK of DMPG and concentrations in the interval 70-300 mM have been investigated by small (SAXS) and wide-angle X-ray scattering, differential scanning calorimetry, and polarized optical microscopy. The order. disorder transition of the hydrocarbon chains occurs along an interval of about 10 degrees C (between T(m)(on) similar to 20 degrees C and T(m)(off) similar to 30 degrees C). Such melting regime was previously characterized at lower concentrations, up to 70 mM DMPG, when sample transparency was correlated with the presence of pores across the bilayer. At higher concentrations considered here, the melting regime persists but is not transparent. Defined SAXS peaks appear and a new lamellar phase L(p) with pores is proposed to exist above 70 mM DMPG, starting at similar to 23 degrees C (similar to 3 degrees C above T(m)(on)) and losing correlation after T(m)(off). A new model for describing the X-ray scattering of bilayers with pores, presented here, is able to explain the broad band attributed to in-plane correlation between pores. The majority of cell membranes have a net negative charge, and the opening of pores across the membrane tuned by ionic strength, temperature, and lipid composition is likely to have biological relevance.

Ab initio calculation of the BCC Fe-Al-Mo (Iron-Aluminum-Molybdenum) phase diagram: Implications for the nature of the tau(2) phase

The metastable phase diagram of the BCC-based ordering equilibria in the Fe-Al-Mo system has been calculated via a truncated cluster expansion, through the combination of Full-Potential-Linear augmented Plane Wave (FP-LAPW) electronic structure calculations and of Cluster Variation Method (CVM) thermodynamic calculations in the irregular tetrahedron approximation. Four isothermal sections at 1750 K, 2000 K, 2250 K and 2500 K are calculated and correlated with recently published experimental data on the system. The results confirm that the critical temperature for the order-disorder equilibrium between Fe(3)Al-D0(3) and FeAl-B2 is increased by Mo additions, while the critical temperature for the FeAl-B2/A2 equilibrium is kept approximately invariant with increasing Mo contents. The stabilization of the Al-rich A2 phase in equilibrium with overstoichiometric B2-(Fe,Mo)Al is also consistent with the attribution of the A2 structure to the tau(2) phase, stable at high temperatures in overstoichiometric B2-FeAl. (C) 2009 Elsevier Ltd. All rights reserved.

Triple Structural Transition below Room Temperature in the Antifilarial Drug Diethylcarbamazine Citrate

A very unusual triple structural transition pattern below room temperature was observed for the antifilarial drug diethylcarbamazine citrate. Besides the first thermal, crystallographic, and vibrational investigations of this first-line drug used in clinical treatment for lymphatic filariasis, a noteworthy behavior with three structural transformations as a function of temperature was demonstrated by differential scanning calorimetry, Raman spectroscopy, and single-crystal X-ray diffractometry. Our X-ray data on single crystals allow for a complete featuring and understanding of all transitions, since the four structures associated with the three solid-solid phase transformations were accurately determined. Two of three structural transitions show an order-disorder mechanism and temperature hysteresis with exothermic peaks at 224 K (T(1)`) and 213 K (T(2)`) upon cooling and endothermic ones at 248 K (T(1)) and 226 K (T(2)) upon heating. The other transition occurs at 108 K (T(3)) and it is temperature-rate sensitive. Molecular displacements onto the (010) plane and conformational changes of the diethylcarbamazine backbone as a consequence of the C-H center dot center dot center dot N hydrogen bonding formation/cleavage between drug molecules explain the mechanism of the transitions at T(1)`/T(2). However, such changes are observed only on alternate columns of the drug intercalated by citrate chains, which leads to a doubling of the lattice period along the a axis of the 235 K structure with respect to the 150 and 293 K structures. At T(2)`/T(1), these structural alterations occur in all columns of the drug. At T(3), there is a rotation on the axis of the N-C bond between the carbamoyl moiety and an ethyl group of one crystallographically independent diethylcarbamazine molecule besides molecular shifts and other conformational alterations. The impact of this study is based on the fascinating finding in which the versatile capability of structural adaptation dependent on the thermal history was observed for a relatively simple organic salt, diethylcarbamazine citrate.

Theoretical Characterization of Hydrogen Polyoxides: HOOH, HOOOH, HOOOOH, and HOOO

We have investigated the polyoxides HOOH, HOOOH, HOOOOH, and HOOO employing the CCSD(T) methodology, and the correlation consistent basis sets. For all molecules, we have computed fundamental vibrational frequencies, structural parameters, rotational constants, and rotation-vibration corrections. For HOOOH, we have obtained a good agreement between our results and microwave and infrared spectra measurements, although for the symmetric OO stretch some important differences were found. Heats of formation were computed using atomization energies, and our recommendation is as follows: Delta H degrees(f,298)(HOOOH) = -21.50 kcal/mol and Delta H degrees(f,298)(HOOOOH) = -10.61 kcal/mol. In the case of HOOO, to estimate the heat of formation, we have constructed three isodesmic reactions to cancel high order correlation effects. The results obtained confirmed that the latter effects are very important for HOOO. The new Delta H degrees(f,298)(HOOO) obtained is 5.5 kcal/mol. We have also calculated the zero-point energies of DO and DOOO to correct the experimental lower limit determined for the Delta H degrees(f,298)(HOOO). The Delta(Delta ZPE) decreases the binding energy of HOOO by 0.56 kcal/mol. Employing the latter value, the new experimental lower limit for Delta H degrees(f,298)(HOOO) is 3.07 kcal/mol, just 2.4 kcal/mol lower than our determination. We expect that the fundamental vibrational frequencies and rotational constants determined for HOOOOH and DOOOOD contribute to its identification in the gas phase. The vibrational spectrum of HOOOOH shows some overlapping with that of HOOOH thus indicating that one may encounter some difficulties in its characterization. We discuss the consequences of the thermochemical properties determined in this work, and suggest that the amount of HOOO present in the atmosphere is smaller than that proposed recently in this journal (J. Phys. Chem A 2007, 111, 4727).

Operacionalização dos objetivos educacionais nos cursos de engenharia

Para a consecução das finalidades de uma disciplina de um curso , várias estratégias de ensino podem ser utilizadas. A estratégia de ensino por objetivos operacionalizados adota, como princípio fundamental, a descrição dos objetivos educacionais em termos do desempenho esperado do aluno e a fixação de padrões mínimos de rendimento aceitável nesse desempenho. A programação de ensino por objetivos operacionalizados deve ser dada a conhecer ao educando, e deve servir de base para o planejamento das atividades docentes e discentes , orientando o aluno nos seus esforços para aprender, e o professor na escolha das técnicas e recursos de ensino que permitam tornar o ensino eficaz. Os resultados da pesquisa empírica realizada mostram que, no nível de efeito principal, o ensino por objetivos operacionalizados é ligeiramente superior ao ensino tradicional . Três turmas foram objeto do experimento, cujo propósito foi comparar , no ensino de Geometria Descritiva, a eficácia relativa das estratégias de ensino com programação por objetivos operacionalizados e a do ensino tradicional. Resultaram os Índices representativos daquela variável: 5,63 para o ensino tradicional, 7,48 para o ensino por objetivos operacionalizados com programação rígida e 7,29 para o ensino por objetivos operacionalizados em que os alunos tiveram liberdade de alguns dos objetivos educacionais. Fortes efeitos de interação foram detectados entre a variável Estratégia de Ensino e as variáveis Escores do Concurso Vestibular, Caracterização Sócio-Econômica e Cultural e Assiduidade, mostrando que, para algumas categorias de alunos, o ensino por objetivos operacionalizados tem rendimento significativamente maior que o ensino tradicional. Os resultados mostram que para algumas categorias a liberdade dada ao aluno para escolher alguns dos objetivos educacionais prejudica o seu nível de aproveitamento no curso, relativamente à mesma estratégia de ensino, porém, com programação totalmente fixada pelo professor. Mesmo nesses casos, o rendimento do ensino por objetivos operacionalizados revela-se superior ao do ensino tradicional.

Efeitos de segunda e terceira ordem da ionosfera no posicionamento GNSS no Brasil

O Sistema de Posicionamento Global (GPS) transmite seus sinais em duas freqüências, o que permite eliminar matematicamente os efeitos de primeira ordem da ionosfera através da combinação linear ionosphere free. Porém, restam os efeitos de segunda e terceira ordem, os quais podem provocar erros da ordem de centímetros nas medidas GPS. Esses efeitos, geralmente, são negligenciados no processamento dos dados GPS. Os efeitos ionosféricos de primeira, segunda e terceira ordem são diretamente proporcionais ao TEC presente na ionosfera, porém, no caso dos efeitos de segunda e terceira ordem, comparecem também o campo magnético da Terra e a máxima densidade de elétrons, respectivamente. Nesse artigo, os efeitos de segunda e terceira ordem da ionosfera são investigados, sendo que foram levados em consideração no processamento de dados GPS na região brasileira para fins de posicionamento. Serão apresentados os modelos matemáticos associados a esses efeitos, as transformações envolvendo o campo magnético da Terra e a utilização do TEC advindo dos Mapas Globais da Ionosfera ou calculados a partir das observações GPS de pseudodistância. O processamento dos dados GPS foi realizado considerando o método relativo estático e cinemático e o posicionamento por ponto preciso (PPP). Os efeitos de segunda e terceira ordem foram analisados considerando períodos de alta e baixa atividade ionosférica. Os resultados mostraram que a não consideração desses efeitos no posicionamento por ponto preciso e no posicionamento relativo para linhas de base longas pode introduzir variações da ordem de poucos milímetros nas coordenadas das estações, além de variações diurnas em altitude da ordem de centímetros.

Photoluminescence of barium-calcium titanates obtained by the microwave-assisted hydrothermal method (MAH)

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

Strutural and optical approach of CdS@ZnS core-shell system

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Programa de Erradicação do Trabalho Infantil (PETI) em Natal: uma avaliação na perspectiva da Assistência Social

This research deals with children and teenagers who are in childish work situation like juridical and institutional conquests connected with public politics in order to effects rights and social support about childish work eradication program (PETI) in terms of evaluation context under social work. The analysis of this research records the PETI implantation process at social nucleus in Cidade Nova (Natal/RN) to absorb children and teenagers who come from lixão . It does this based on the two thousands (2005) and presents the program importance linking users and their families such as the investigation of PETI actions, intending to give a contribution in the childish work combat and how they have been developed social-education protection for children and teenagers (seven to fifteens). About quality and quantity it was make a survey of social-economical characterization of the people benefits (to families) through interviews with users. This study (make us) sure brings new subventions which can cooperate to the childish work eradication by others public politics articulations

Programa de Erradicação do Trabalho Infantil (PETI) em Natal: uma avaliação na perspectiva da Assistência Social

This research deals with children and teenagers who are in childish work situation like juridical and institutional conquests connected with public politics in order to effects rights and social support about childish work eradication program (PETI) in terms of evaluation context under social work. The analysis of this research records the PETI implantation process at social nucleus in Cidade Nova (Natal/RN) to absorb children and teenagers who come from lixão . It does this based on the two thousands (2005) and presents the program importance linking users and their families such as the investigation of PETI actions, intending to give a contribution in the childish work combat and how they have been developed social-education protection for children and teenagers (seven to fifteens). About quality and quantity it was make a survey of social-economical characterization of the people benefits (to families) through interviews with users. This study (make us) sure brings new subventions which can cooperate to the childish work eradication by others public politics articulations

Intense visible photoluminescence in Ba(Zr0.25Ti0.75)O-3 thin films

Photoluminescence at room temperature in Ba(Zr0.25Ti0.75)O-3 thin films was explained by the degree of structural order-disorder. Ultraviolet-visible absorption spectroscopy, photoluminescence, and first principles quantum mechanical measurements were performed. The film annealed at 400 degrees C for 4 h presents intense visible photoluminescence behavior at room temperature. The increase of temperature and annealing time creates [ZrO6]-[TiO6] clusters in the lattice leading to the trapping of electrons and holes. Thus, [ZrO5]-[TiO6]/[ZrO6]-[TiO6] clusters were the main reason for the photoluminescence behavior.

Combined experimental and theoretical investigations of the photoluminescent behavior of Ba(Ti,Zr)O-3 thin films

The correlation between experimental data and theoretical calculations have been investigated to explain the photoluminescence at room temperature of Ba(Ti0.75Zr0.25)O-3 (BTZ) thin films prepared by the polymeric precursor method. The degree of structural order-disorder was investigated by X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible absorption spectroscopy and photoluminescence (PL) measurements. First-principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and deformed asymmetric models. The electronic properties are analyzed and the relevance of the present theoretical and experimental results on the PL behavior is discussed. The presence of localized electronic levels and a charge gradient in the band gap due to a break in symmetry, are responsible for the PL in disordered BTZ lattice. (c) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Voltage-composition profile and synchrotron X-ray structural analysis of low and high temperature LixCoO2 host material

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