Synthesis of optically complex core-shell colloidal suspensions: Pathways to multiplexed biological screening

The ability to generate enormous random libraries of DNA probes via split-and-mix synthesis on solid supports is an important biotechnological application of colloids that has not been fully utilized to date. To discriminate between colloid-based DNA probes each colloidal particle must be 'encoded' so it is distinguishable from all other particles. To this end, we have used novel particle synthesis strategies to produce large numbers of optically encoded particle suitable for DNA library synthesis. Multifluorescent particles with unique and reproducible optical signatures (i.e., fluorescence and light-scattering attributes) suitable for high-throughput flow cytometry have been produced. In the spectroscopic study presented here, we investigated the optical characteristics of multi-fluorescent particles that were synthesized by coating silica 'core' particles with up to six different fluorescent dye shells alternated with non-fluorescent silica 'spacer' shells. It was observed that the diameter of the particles increased by up to 20% as a result of the addition of twelve concentric shells and that there was a significant reduction in fluorescence emission intensities from inner shells as an increasing number of shells were deposited.

The preparation of zinc(II) and cadmium(II) complexes of the pentadentate N3S2 ligand formed from 2,6-diacetylpyridine and S-benzyldithiocarbazate (H2SNNNS) and the X-ray crystal structure of the novel dimeric [Zn2(SNNNS)2] complex

The pentadentate chelating agent, 2,6-diacetylpyridinebis(S-benzyldithiocarbazate) (H2SNNNS) reacts with zinc(II) and cadmium(II) ions forming stable complexes of empirical formula, [M(SNNNS)] (M=Zn2+, Cd2+; SNNNS2 =doubly deprotonated anionic form of the Schiff base). These complexes have been characterized by a variety of physico-chemical techniques. IR and H-1 NMR spectral evidence indicate that the Schiff base coordinates to the zinc(II) and cadmium(II) ions via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the mercaptide sulfur atoms. The crystal and molecular structure of the zinc(II) complex has been determined by X-ray diffraction. The complex is a dimer in which the pyridine nitrogen atom,the azomethine nitrogen atom and the thiolate sulfur atom from one ligand coordinate to one of the zinc(II) ions whereas the azomethine and thiolate sulfur atoms from another ligand complete pentacoordination around the zinc(II) ion, the ligands being coordinated in their deprotonated forms. The coordination geometry about each zinc(II) can be considered as intermediate between a square-pyramid and trigonal-bipyramid. The cadmium(II) complex is also assigned with a dimeric structure. (C) 2003 Elsevier Ltd. All rights reserved.

Rates of electronic energy transfer in conformationally flexible bichromophoric macrocyclic complexes: a combined experimental and molecular modeling study

Electronic energy transfer (EET) rate constants between a naphthalene donor and anthracene acceptor in [ZnL4a](ClO4)(2) and [ZnL4b](ClO4)(2) were determined by time-resolved fluorescence where L-4a and L-4b are the trans and cis isomers of 6-((anthracen-9-yl-methyl)amino)-6,13-dimethyl-13-((naphthalen-1-yl-methyl)amino)-1,4,8,11-tetraazacyclotetradecane, respectively. These isomers differ in the relative disposition of the appended chromophores with respect to the macrocyclic plane. The trans isomer has an energy transfer rate constant (k(EET)) of 8.7 x 10(8) s(-1), whereas that of the cis isomer is significantly faster (2.3 x 10(9) s(-1)). Molecular modeling was used to determine the likely distribution of conformations in CH3CN solution for these complexes in an attempt to identify any distance or orientation dependency that may account for the differing rate constants observed. The calculated conformational distributions together with analysis by H-1 NMR for the [ZnL4a](2+) trans complex in the common trans-III N-based isomer gave a calculated Forster rate constant close to that observed experimentally. For the [ZnL4b](2+) cis complex, the experimentally determined rate constant may be attributed to a combination of trans-Ill and trans-I N-based isomeric forms of the complex in solution.

Simbolismos e motivação no trabalho voluntário:um estudo de caso na Associação de voluntários da APAE de Venda Nova do Imigrante

O objetivo dessa pesquisa é: Compreender os aspectos simbólicas que se relacionam com a motivação no trabalho voluntário na Associação de Voluntários da APAE de Venda Nova do Imigrante - AVAPAE. Para isso, os investigadores apoiam-se na relevância de se estudar as organizações através de abordagens que envolvem a problemática do estudo do simbolismo com intuito de entender as organizações por caminhos diferentes ás teorias organizacionais dominantes, como o funcionalismo. O simbolismo organizacional (MORGAN; FROST; PONDY, 1983; GIOIA, 1986; CARRIERI, 2007) é compreendido como uma teoria organizacional, e o paradigma interpretativo (MORGAN; FROST; PONDY,1983) está posicionado como uma importante abordagem na busca por entender tantos os aspectos formais como os aspectos informais de uma organização. A Teoria das Representações Sociais (MOSCOVICI, 2003) foi adotada como base para investigar essas interpretações em uma organização, com o intuito de alçar uma análise mais aprofundada da vida cotidiana e dos aspectos simbólicos que constroem esse cotidiano, a partir da aplicação da análise de conteúdo (BARDIN, 1977). O entendimento do que motiva o voluntário a exercer sua atividade foi ancorado na construção social dessa realidade (BERGER; LUCKMANN, 1985) estudada, que se baseia na representação do fenômeno motivação do trabalho pela abordagem da subjetividade (REY, 2003) do indivíduo em relação ao seu ambiente de trabalho. A pesquisa pôde chegar a resultados através de uma análise interpretativa simbólica, em um entendimento de que a realidade da AVAPAE se mostrou complexa e subjetiva, levando à identificação de uma relevante influência da construção simbólica da cidade em que a AVAPAE atua, Venda Nova do Imigrante. Assim, a partir desse diagnóstico se evidenciou a interferência dos valores do cidadão vendanovense enquanto produto e produtor dos simbolismos que envolvem o voluntariado. Como contribuição final deste trabalho, defende-se que os caminhos para tratar dessas questões devem considerar a subjetividade que as permeia como um sistema aberto, em uma expressão constante da ação do indivíduo e do contexto social em que ele vive, sendo essa relação uma troca contínua por meio das relações simbólicas vivenciadas pelo ator social e o grupo em que convive.

O prêmio INOVES : a sociologia de um sucesso

A litania conhecida relata muito mais sobre maus governos, principalmente, em países em desenvolvimento, do que sobre suas práticas inovadoras. Nas agências brasileiras nos últimos anos assiste-se a presença constante e reiterada da ideia de uma reforma administrativa. A observação mais simples tem mostrado baixos níveis de eficiência, efetividade e transparência nas instituições públicas. O presente estudo visa expor, na contramão do senso comum, um exemplo de bom governo – o Prêmio INOVES. Dessa maneira levantam-se os conceitos de eficiência e efetividade no setor público. Bem como, a exposição de um cenário do estado do Espírito Santo que se mostra aberto as perspectivas de mudança. Por intermédio da sociologia das organizações, busca-se aspectos da realidade das experiências apresentadas pelo prêmio INOVES, para explicar, a partir de conceitos particulares da teoria das relações humanas e na digressão dos modelos da ação concreta de Crozier e Friedberg (1977) a análise da ação/situação das condutas dos atores envolvidos em projetos vencedores. A metodologia utilizada no desenho dessa pesquisa é aquela ligada a Ground Theory de Strauss (1967), o qual enfatiza que a construção do conhecimento sobre determinados objetos deve ser minimamente pensada como articulação de conceitos básicos que iriam nortear o vai e vem entre a observação – seja etnográfica ou de entrevista em profundidade – e a confirmação e reconstrução em um plano mais complexo da teoria a ser aplicada. A conclusão mais imediata aos estudos realizados perpassa as teorias de alcance médio que permitem um contato com o objeto de estudo, cuja proximidade permite um processo de descoberta da relevância dos pontos centrais a observação, bem como um outro pilar teórico das investigações, sobre os atores envolvidos na cooperação interna dos projetos.

Applying complex network theory to the understanding of high-aspect-ratio carbon-filled composites

This work demonstrates that the theoretical framework of complex networks typically used to study systems such as social networks or the World Wide Web can be also applied to material science, allowing deeper understanding of fundamental physical relationships. In particular, through the application of the network theory to carbon nanotubes or vapour-grown carbon nanofiber composites, by mapping fillers to vertices and edges to the gap between fillers, the percolation threshold has been predicted and a formula that relates the composite conductance to the network disorder has been obtained. The theoretical arguments are validated by experimental results from the literature.

As formas de participação na construção do projecto político pedagógico : diferentes realidades escolares

RESUMO: Na sociedade da comunicação e da informação, as escolas ainda não conseguiram compreender o seu papel de facilitadoras do conhecimento que o mundo está promovendo entre a realidade da escola e o interesse do educando. Um dos fatores para isso é o crescimento das escolas ao longo dos séculos e a necessidade de superação decorrente do alargamento da educação, que têm gerado um conhecimento complexo que descreve as reflexões e conscientizações sobre o nosso próprio desenvolvimento humano e sobre a nossa participação no mundo em que estamos vivendo. Essas complexidades possibilitam mudanças, principalmente nas questões epistemológicas e paradigmáticas, que proporcionaram outra forma de conceber o conhecimento e os saberes, chamado de “ecologia dos saberes”. Nesse contexto, existe a necessidade de se fazer uma leitura crítica na e da escola e de sua participação junto à comunidade escolar, objetivando minimizar as relações de dominação, de normatizações, de disciplinamento, de concentração de poder, para direcionar a educação num processo emancipatório, democrático, consciente das mudanças, de forma a incluir todos os saberes possíveis para acompanhar e valorizar a realidade escolar, através da participação de alta intensidade na construção e reconstrução do seu projeto político pedagógico. Para tanto, iremos discorrer sobre três escolas, a partir da análise de cada uma dentro da realidade construída por elas, buscando demonstrar que as escolas, dentro dos seus contextos educacionais, possuem diferentes realidades que não podem ser generalizadas, mas que devem ser compreendidas no sentido de que sejam promovidas a autonomia escolar e o fortalecimento da democracia educacional, objetivando a superação das condições atuais da educação para se adequar à sociedade e ao mundo atual. ABSTRACT: In the present society of communication and information, schools have not yet been able to understand their roles as facilitators of the knowledge that the world is promoting between the reality of school and the interest of the learner. One of the reasons for that is the growth of schools along the centuries as well as their constant need for getting over old problems, due to the expansion of education. These questions lead to a complex knowledge which describes reflections on our own human development and on our participation in the world we live in. These complexities lead to changes, especially in epistemological and paradigmatic questions, making it possible for new ways of conceiving knowledge, known as “ecology of knowledge”. In this context, there is a need for making a critical reading about school and its participation in the school community, with the objective to minimize the relations of domination, power concentration and discipline and to direct education towards a process of emancipation and democracy, in which there is conscience of the necessary changes to include all possible knowledge as a way to value the reality of school through a high intensity participation in the construction and reconstruction of its political and pedagogical project. Thus, this study will discuss three schools, basing this discussion on the analysis of each school within the reality built by them, trying to demonstrate that, within their educational contexts, each one possesses different realities that cannot be generalized. These differences must, however, be understood, in order to allow the promotion of school autonomy and the strengthening of educational democracy with the objective to get over education`s present conditions and adjust them to society and to the present world.

Peroral susceptibility of Aedes albifasciatus and Culex pipiens complex mosquitoes (Diptera: Culicidae) from Argentina to western equine encephalitis virus

The transmission cycle of western equine encephalitis (WEE) virus in South America is unknown. A WEE virus strain was isolated from Aedes albifasciatus in Argentina during the WEE epizootic of 1982-83. Also, Culex pipiens from Argentina was reported to be able to transmit WEE virus experimentally, but other results indicate that Cx. pipiens from the USA is refractory to this virus. We determined the susceptibility of Argentina strains of Ae. albifasciatus and Culex pipiens complex mosquites to infection by WEE virus by the oral route. Adult females were fed on chicks infected with a WEE virus strain isolated in Cordoba Province, Argentina, or were fed on a blood/virus suspension. Each mosquito ingested between 10(1.6) to 10(6.4) vero cell plaque-forming units of virus. Each of 28 Ae. albifasciatus was positive for virus from the fourth day postfeeding, and there was evidence for virus replication. In contrast, 0/44 Cx. p. quinquefasciatus and only 1/15 Cx. p. pipiens was positive. Aedes albifasciatus is susceptible to infection by WEE virus and should be considered a potential vector of this virus in Argentina. Both subspecies of Cx. pipiens are refractory to peroral infection by WEE virus and probably do not play a role in the WEE virus cycle in Argentina.

A systematic procedure to enhance reproducibility of SWASV cycles in the determination of toxic metals in real samples

This work presents for the first time a systematic study on the optimization of the electrochemical cleaning time of a mercury film when it is used as a working electrode material in the analysis of toxic metals, such as Pb2+, used as model metal, in real samples by SWASV. The optimization study for the film’s cleaning time aimed at attaining a Pb2+ minimum value in the film after the re-oxidation step of the pre-concentrated metal, given the impossibility of complete removal of traces of the electroactive species from the film. This value was kept constant in each concentration range studied ensuring thus that all assays were performed in initial identical conditions. An assay performed on a synthetic sample was taken as reference. In it, given the absence of matrix effects, and after the electrochemical cleaning step, a direct proportionality was observed between the residual amounts of Pb2+ in the film (which for the cleaning time used was never completely removed) and Pb2+ concentration in the solution. This fact determined a high correlation between Pb2+ peak current and Pb2+ concentration which was not observed when real samples (tree leaves) were analyzed. This behavior may result from the presence of the interfering surfactants always present in real samples of complex matrix. Cleaning time optimization was performed for the following Pb2+ concentration ranges in the real samples of complex matrix: 0.006-0.020, 0.020-0.080, 0.060-0.200 and 0.100-0.600 ppb. As expected, in order to obtain identical levels of film’s cleaning efficiency, the need for longer cleaning times has been observed for higher concentrations. The optimized cleaning times for the concentration ranges under study were 120, 150, 180 e 300 s, respectively.

On differentiability and analyticity of positive definite functions

We derive a set of differential inequalities for positive definite functions based on previous results derived for positive definite kernels by purely algebraic methods. Our main results show that the global behavior of a smooth positive definite function is, to a large extent, determined solely by the sequence of even-order derivatives at the origin: if a single one of these vanishes then the function is constant; if they are all non-zero and satisfy a natural growth condition, the function is real-analytic and consequently extends holomorphically to a maximal horizontal strip of the complex plane.

Extraction of hemoglobin with calixarenes and biocatalysis in organic media of the complex with pseudoactivity of peroxidase

The present work involves the use of p-tert-butylcalix[4,6,8]arene carboxylic acid derivatives ((t)Butyl[4,6,8]CH2COOH) for selective extraction of hemoglobin. All three calixarenes extracted hemoglobin into the organic phase, exhibiting extraction parameters higher than 0.90. Evaluation of the solvent accessible positively charged amino acid side chains of hemoglobin (PDB entry 1XZ2) revealed that there are 8 arginine, 44 lysine and 30 histidine residues on the protein surface which may be involved in the interactions with the calixarene molecules. The hemoglobin-(t)Butyl[6]CH2COOH complex had pseudoperoxidase activity which catalysed the oxidation of syringaldazine in the presence of hydrogen peroxide in organic medium containing chloroform. The effect of pH, protein and substrate concentrations on biocatalysis was investigated using the hemoglobin-(t)Butyl[6]CH2COOH complex. This complex exhibited the highest specific activity of 9.92 x 10(-2) U mg protein(-1) at an initial pH of 7.5 in organic medium. Apparent kinetic parameters (V'(max), K'(m), k'(cat) and k'(cat)/K'(m)) for the pseudoperoxidase activity were determined in organic media for different pH values from a Michaelis-Menten plot. Furthermore, the stability of the protein-calixarene complex was investigated for different initial pH values and half-life (t(1/2)) values were obtained in the range of 1.96 and 2.64 days. Hemoglobin-calixarene complex present in organic medium was recovered in fresh aqueous solutions at alkaline pH, with a recovery of pseudoperoxidase activity of over 100%. These results strongly suggest that the use of calixarene derivatives is an alternative technique for protein extraction and solubilisation in organic media for biocatalysis.

Organization knowledge management change from a complex adaptive systems perpective with ability for ambidexeterity

We are working on the confluence of knowledge management, organizational memory and emergent knowledge with the lens of complex adaptive systems. In order to be fundamentally sustainable organizations search for an adaptive need for managing ambidexterity of day-to-day work and innovation. An organization is an entity of a systemic nature, composed of groups of people who interact to achieve common objectives, making it necessary to capture, store and share interactions knowledge with the organization, this knowledge can be generated in intra-organizational or inter-organizational level. The organizations have organizational memory of knowledge of supported on the Information technology and systems. Each organization, especially in times of uncertainty and radical changes, to meet the demands of the environment, needs timely and sized knowledge on the basis of tacit and explicit. This sizing is a learning process resulting from the interaction that emerges from the relationship between the tacit and explicit knowledge and which we are framing within an approach of Complex Adaptive Systems. The use of complex adaptive systems for building the emerging interdependent relationship, will produce emergent knowledge that will improve the organization unique developing.

Biochemical and structural characterization of β-lactamases tem-180 and tem-201

With the constant development of new antibiotics, selective pressure is a force to reckon when investigating antibiotic resistance. Although advantageous for medical treatments, it leads to increasing resistance. It is essential to use more potent and toxic antibiotics. Enzymes capable of hydrolyzing antibiotics are among the most common ways of resistance and TEM variants have been detected in several resistant isolates. Due to the rapid evolution of these variants, complex phenotypes have emerged and the need to understand their biological activity becomes crucial. To investigate the biochemical properties of TEM-180 and TEM-201 several computational methodologies have been used, allowing the comprehension of their structure and catalytic activity, which translates into their biological phenotype. In this work we intent to characterize the interface between these proteins and the several antibiotics used as ligands. We performed explicit solvent molecular dynamics (MD) simulations of these complexes and studied a variety of structural and energetic features. The interfacial residues show a distinct behavior when in complex with different antibiotics. Nevertheless, it was possible to identify some common Hot Spots among several complexes – Lys73, Tyr105 and Glu166. The structural changes that occur during the Molecular Dynamic (MD) simulation lead to the conclusion that these variants have an inherent capacity of adapting to the various antibiotics. This capability might be the reason why they can hydrolyze antibiotics that have not been described until now to be degraded by TEM variants. The results obtained with computational and experimental methodologies for the complex with Imipenem have shown that in order to this type of enzymes be able to acylate the antibiotics, they need to be capable to protect the ligand from water molecules.

Biodegradation rate constants in different NF/UF fractions of cork processing wastewaters

Cork processing wastewater is an aqueous complex mixture of organic compounds that have been extracted from cork planks during the boiling process. These compounds, such as polysaccharides and polyphenols, have different biodegradability rates, which depend not only on the natureof the compound but also on the size of the compound. The aim of this study is to determine the biochemical oxygen demands (BOD) and biodegradationrate constants (k) for different cork wastewater fractions with different organic matter characteristics. These wastewater fractions were obtained using membrane separation processes, namely nanofiltration (NF) and ultrafiltration (UF). The nanofiltration and ultrafiltration membranes molecular weight cut-offs (MWCO) ranged from 0.125 to 91 kDa. The results obtained showed that the biodegradation rate constant for the cork processing wastewater was around 0.3 d(-1) and the k values for the permeates varied between 0.27-0.72 d(-1), being the lower values observed for permeates generated by the membranes with higher MWCO and the higher values observed for the permeates generated by the membranes with lower MWCO. These higher k values indicate that the biodegradable organic matter that is permeated by the membranes with tighter MWCO is more readily biodegradated.

Complex fluids at complex surfaces simply complicated

We study wetting and filling of patterned surfaces by a nematic liquid crystal. We focus on three important classes of periodic surfaces: triangular, sinusoidal and rectangular. The results highlight the similarities and differences of nematic wetting of these surfaces and wetting by simple fluids. The interplay of geometry, surface and elastic energies can lead to the suppression of either filling or wetting. The periodic rectangular surface displays re-entrant transitions, with a sequence dry-filled-wet-filled, in the relevant region of parameter space.