A análise por injeção sequencial (SIA): vinte anos em uma perspectiva brasileira

The year of 2010 marks the 20th anniversary of the development of Sequential Injection Analysis (SIA) by Ruzicka and Marshall. Considered the second generation of the flow injection methods, this article briefly describes the history, the basic principles of the technique and reviews all papers developed by Brazilian scientists aiming the divulgation of this automation technique in Analytical Chemistry.

Photophysical studies and in vitro skin permeation/retention of Foscan (R)/nanoemulsion (NE) applicable to photodynamic therapy skin cancer treatment.

In this work we evaluated the photophysical and in vitro properties of Foscan (R), a second-generation photosensitizer drug (PS) widely used in systemic clinical protocols for cancer therapy based on Photodynamic Therapy (PDT). We employed biodegradable nanoemulsions (NE) as a colloidal vehicle of the oil/water (o/w) type focusing in topical administration of Foscan (R) and other photosensitizer drugs. This formulation was obtained and stabilized by the methodology described by Tabosa do Egito et al.,(30) based on the mixture of two phases: an aqueous solution and an organic medium consisting of nonionic surfactants and oil. The photodynamic potential of the drug incorporated into the NE was studied by steady-state and time-resolved spectroscopic techniques. We also analyzed the in vitro biological behavior carried out in mimetic biological environment protocols based on the animal model. After topical application in a skin animal model, we evaluated the Foscan (R)/NE diffusion flux into the skin layers (stratum corneum and epidermis + dermis) by classical procedures using Franz Diffusion cells. Our results showed that the photophysical properties of PS were maintained after its incorporation into the NE when compared with homogeneous organic medium. The in vitro assays enabled the determination of an adequate profile for the interaction of this system in the different skin layers, with an ideal time lag of 6 h after topical administration in the skin model. The Foscan (R) diffusion flux (J) was increased when this PS was incorporated into the NE, if compared with its flux in physiological medium. These parameters demonstrated that the NE can be potentially applied as a drug delivery system (DDS) for Foscan (R) in both in vitro and in vivo assays, as well as in future clinical applications involving topical skin cancer PDT.

Evaluation of ductus venosus and inferior vena cava by using multiple Doppler ultrasound parameters in healthy fetuses

The objective of this study was to describe multiple Doppler ultrasound parameters of ductus venosus and inferior vena cava in fetuses at gestational ages ranging from 22 to 38 weeks. In this prospective observational study, Doppler ultrasound exams were performed in 45 healthy fetuses at 22, 26, 34, and 38 weeks. Maximum venous velocity, minimum venous velocity, venous pulsatility index, and venous acceleration time (VAT) (defined as the time between minimum and maximum venous velocity) were evaluated at those gestational periods. Increase in the velocities and decrease in the pulsatility index were observed in these vessels throughout gestational age. The VAT increased with gestational age. The VAT, a Doppler parameter still not described elsewhere, increased during pregnancy could be related to a longer period of time needed to fill the atrium in bigger hearts. In this study, we provide reference values for VAT in healthy fetuses.

Theory of nitride oxide adsorption on transition metal (111) surfaces: a first-principles investigation

In this work, we report a density functional theory study of nitric oxide (NO) adsorption on close-packed transition metal (TM) Rh(111), Ir(111), Pd(111) and Pt(111) surfaces in terms of adsorption sites, binding mechanism and charge transfer at a coverage of Theta(NO) = 0.25, 0.50, 0.75 monolayer (ML). Based on our study, an unified picture for the interaction between NO and TM(111) and site preference is established, and valuable insights are obtained. At low coverage (0.25 ML), we find that the interaction of NO/TM(111) is determined by an electron donation and back-donation process via the interplay between NO 5 sigma/2 pi* and TM d-bands. The extent of the donation and back-donation depends critically on the coordination number (adsorption sites) and TM d-band filling, and plays an essential role for NO adsorption on TM surfaces. DFT calculations shows that for TMs with high d-band filling such as Pd and Pt, hollow-site NO is energetically the most favorable, and top-site NO prefers to tilt away from the normal direction. While for TMs with low d-band filling (Rh and Ir), top-site NO perpendicular to the surfaces is energetically most favorable. Electronic structure analysis show that irrespective of the TM and adsorption site, there is a net charge transfer from the substrate to the adsorbate due to overwhelming back-donation from the TM substrate to the adsorbed NO molecules. The adsorption-induced change of the work function with respect to bare surfaces and dipole moment is however site dependent, and the work function increases for hollow-site NO, but decreases for top-site NO, because of differences in the charge redistribution. The interplay between the energetics, lateral interaction and charge transfer, which is element dependent, rationalizes the structural evolution of NO adsorption on TM(111) surfaces in the submonolayer regime.

Aspectos conceituais da regulação dos serviços de água e esgoto no Brasil

Objetiva-se, aqui, apresentar os aspectos conceituais da regulação da prestação dos serviços de água e esgoto no Brasil e analisar de forma comparativa essa regulação com a de outros setores da infraestrutura. O estudo parte do pressuposto da regulação como intervenção do Estado voltada para a eficiência e a equidade, e apresenta os fundamentos teóricos que justificam essa regulação de forma contextualizada às características do setor de água e esgoto. Mediante análise comparativa com outros setores de infraestrutura de redes, concluí-se que, em função das características físicas, econômicas e institucionais do setor de água e esgoto, será bastante complexo o estabelecimento efetivo dessa atividade conforme os princípios da lei nº 11.445/2007.

Gerenciamento participativo em saúde do trabalhador: uma experiência na atividade de controle de vetores

Este artigo apresenta a experiência de implantação de um sistema de gestão em Saúde do Trabalhador implantado na Superintendencia de Controle de Endemias (SUCEN), no período de 1998 a 2002, que operava na atividade de controle químico de vetores no Estado de São Paulo. OBJETIVO: Descrever o sistema de gestão participativa, as ações desenvolvidas e os principais resultados alcançados. MÉTODO: Relato da experiência vivenciada pela equipe usando abordagem qualitativa, análise de documentos e apresentação de dados quantitativos. RESULTADOS: Foram eleitas 11 Comissões de Saúde e Trabalho (COMSAT's) que em conjunto com a equipe técnica iniciaram a identificação dos riscos e de propostas para prevenção e controle dos riscos no trabalho. O mapeamento de riscos resultou em 650 recomendações, 45,7% das quais foram executadas. Foram identificadas como doenças relacionadas ao trabalho: reações alérgicas aos pesticidas, lesões por esforços repetitivos, distúrbios auditivos e patologias de coluna vertebral. Participaram dos cursos básicos de saúde do trabalhador 1.003 servidores (76,3% do total de servidores), sendo que 90,8% dos participantes os consideraram ótimos ou bons. CONCLUSÕES: O sistema de gerenciamento participativo coloca em prática os princípios de gestão democrática do Sistema Único de Saúde (SUS); incorpora, por meio do mapeamento de riscos, o saber do trabalhador; inclui os trabalhadores como sujeitos do processo de negociação e mudanças; pratica o direito à informação. As COMSAT's revelaram-se espaços adequados para a negociação das melhorias nas condições de trabalho. A aprovação do sistema de gestão culminou na validação legal por meio de um acordo tripartite assinado em março de 2002.

First Report on Rotenoids as Neurotoxic Principles of Seeds from Aeschynomene indica (Leguminosae)

Toxic principles from seeds of Aeschynomene indica collected in Brazil were analyzed. Dalpanol, 12 alpha-hydroxydalpanol and 11-hydroxydalpanol were identified using (1)H NMR in A. indica for the first time. 11-hydroxydalpanol has not been previously reported in the existing literature. Furthermore these rotenoids are likely the toxic principles that cause neurological signs in mice.

Unraveling effects of disorder on the electronic structure of SiO(2) from first principles

We present a first-principles systematic study of the electronic structure of SiO(2) including the crystalline polymorphs alpha quartz and beta cristobalite, and different types of disorder leading to the amorphous phase. We start from calculations within density functional theory and proceed to more sophisticated quasiparticle calculations according to the GW scheme. Our results show that different origins of disorder have also different impact on atomic and electronic-density fluctuations, which affect the electronic structure and, in particular, the size of the mobility gap in each case.

Quantum confinement effects on Mn-doped InAs nanocrystals: A first-principles study

We studied the effect of quantum confinement in Mn-doped InAs nanocrystals using theoretical methods. We observe that the stability of the impurities decreases with the size of the nanocrystals, making doping more difficult in small nanoparticles. Substitutional impurities are always more stable than interstitial ones, independent of the size of the nanocrystal. There is also a decrease in the energy difference between the high and low spin configurations, indicating that the critical temperature should decrease with the size of the nanoparticles, in agreement with experimental observations and in detriment to the development of functional spintronic devices with doped nanocrystals. Codoping with acceptors or saturating the nanocrystals with molecules that insert partially empty levels in the energy gap should be an efficient way to increase T(C).

Optical absorption and electronic band structure first-principles calculations of alpha-glycine crystals

Light absorption of alpha-glycine crystals grown by slow evaporation at room temperature was measured, indicating a 5.11 +/- 0.02 eV energy band gap. Structural, electronic, and optical absorption properties of alpha-glycine crystals were obtained by first-principles quantum mechanical calculations using density functional theory within the generalized gradient approximation in order to understand this result. To take into account the contribution of core electrons, ultrasoft and norm-conserving pseudopotentials, as well as an all electron approach were considered to compute the electronic density of states and band structure of alpha-glycine crystals. They exhibit three indirect energy band gaps and one direct Gamma-Gamma energy gap around 4.95 eV. The optical absorption related to transitions between the top of the valence band and the bottom of the conduction band involves O 2p valence states and C, O 2p conduction states, with the carboxyl group contributing significantly to the origin of the energy band gap. The calculated optical absorption is highly dependent on the polarization of the incident radiation due to the spatial arrangement of the dipolar glycine molecules; in the case of a polycrystalline sample, the first-principles calculated optical absorption is in good agreement with the measurement when a rigid energy shift is applied.

First-principles study of the adsorption of atomic and molecular hydrogen on BC(2)N nanotubes

The adsorption of atomic and molecular hydrogen on armchair and zigzag boron carbonitride nanotubes is investigated within the ab initio density functional theory. The adsorption of atomic H on the BC(2)N nanotubes presents properties which are promising for nanoelectronic applications. Depending on the adsorption site for the H, the Fermi energy moves toward the bottom of the conduction band or toward the top of the valence band, leading the system to exhibit donor or acceptor characteristics, respectively. The H(2) molecules are physisorbed on the BC(2)N surface for both chiralities. The binding energies for the H(2) molecules are slightly dependent on the adsorption site, and they are near to the range to work as a hydrogen storage medium.

Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

The notion of structure and the information records of the documentary systems

Assuming as a starting point the acknowledge that the principles and methods used to build and manage the documentary systems are disperse and lack systematization, this study hypothesizes that the notion of structure, when assuming mutual relationships among its elements, promotes more organical systems and assures better quality and consistency in the retrieval of information concerning users` matters. Accordingly, it aims to explore the fundamentals about the records of information and documentary systems, starting from the notion of structure. In order to achieve that, it presents basic concepts and relative matters to documentary systems and information records. Next to this, it lists the theoretical subsides over the notion of structure, studied by Benveniste, Ferrater Mora, Levi-Strauss, Lopes, Penalver Simo, Saussure, apart from Ducrot, Favero and Koch. Appropriations that have already been done by Paul Otlet, Garcia Gutierrez and Moreiro Gonzalez. In Documentation come as a further topic. It concludes that the adopted notion of structure to make explicit a hypothesis of real systematization achieves more organical systems, as well as it grants pedagogical reference to the documentary tasks.