Solvation dynamics in nonassociated polar solvents

Ultrafast solvation dynamics in three nonassociated polar solvents, namely, acetonitrile, dimethyl sulfoxide, and acetone, have been studied by using the molecular hydrodynamic theory. For solvation in acetonitrile, the solvent memory function required for this study has been obtained from recent dielectric relaxation measurements of Venabales and Schuttenmaer; earlier theoretical studies used only the Kerr relaxation data. As the latter provides only an indirect information regarding the polar dynamical response of the dipolar liquid, it fails to provide a fully quantitative description of the solvation time correlation function, S(t). The present study with full dielectric data, on the other hand, gives excellent agreement with the experimental results. The theory shows that the ultrafast part of the solvation dynamics originates almost entirely from the high-frequency component of dielectric relaxation (with time constant 0.177 ps), although the latter represents only a small part of the latter. For DMSO and acetone, however, the present theory predicts a decay slower than the experimental observation. It is proposed that for these two solvents specific chromophore-solvent interactions might be responsible for the-large discrepancy. On the basis of the theory, two experimental studies have also been proposed.

Efficient algorithms for learning kernels from multiple similarity matrices with general convex loss functions

In this paper we consider the problem of learning an n × n kernel matrix from m(1) similarity matrices under general convex loss. Past research have extensively studied the m = 1 case and have derived several algorithms which require sophisticated techniques like ACCP, SOCP, etc. The existing algorithms do not apply if one uses arbitrary losses and often can not handle m > 1 case. We present several provably convergent iterative algorithms, where each iteration requires either an SVM or a Multiple Kernel Learning (MKL) solver for m > 1 case. One of the major contributions of the paper is to extend the well knownMirror Descent(MD) framework to handle Cartesian product of psd matrices. This novel extension leads to an algorithm, called EMKL, which solves the problem in O(m2 log n 2) iterations; in each iteration one solves an MKL involving m kernels and m eigen-decomposition of n × n matrices. By suitably defining a restriction on the objective function, a faster version of EMKL is proposed, called REKL,which avoids the eigen-decomposition. An alternative to both EMKL and REKL is also suggested which requires only an SVMsolver. Experimental results on real world protein data set involving several similarity matrices illustrate the efficacy of the proposed algorithms.

Thin Films of Titanium Dioxide Prepared by Chemical Routes using Novel Precursors

Novel, volatile, stable, oxo-β-ketoesterate complexes of titanium, whose synthesis requires only an inert atmosphere, as opposed to a glove box, have been developed. Using one of the complexes as the precursor, thin films of TiO2 have been deposited on glass substrates by metalorganic chemical vapor deposition (MOCVD) at temperatures ranging from 400°C to 525°C and characterized by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. All the films grown in this temperature range are very smooth; those grown above 480°C consist of nearly monodisperse, nanocrystals of the anatase phase. Optical studies show the bandgaps in the range 3.4–3.7 eV for films grown at different temperatures. Thin films of anatase TiO2 have also been grown by spin-coating technique using another ketoesterate complex of titanium, demonstrating that the newly developed complexes can be successfully used for thin film growth by various chemical routes.

NanoLAB Triboprobe: Characterizing Dynamic Wear, Friction and Fatigue at the Nanoscale

In-situ transmission electron microscopy (TEM) has developed rapidly over the last decade. In particular, with the inclusion of scanning probes in TEM holders, allows both mechanical and electrical testing to be performed whilst simultaneously imaging the microstructure at high resolution. In-situ TEM nanoindentation and tensile experiments require only an axial displacement perpendicular to the test surface. However, here, through the development of a novel in-situ TEM triboprobe, other surface characterisation experiments are now possible, with the introduction of a fully programmable 3D positioning system. Programmable lateral displacement control allows scratch tests to be performed at high resolution with simultaneous imaging of the changing microstructure. With the addition of repeated cyclic movements, both nanoscale fatigue and friction experiments can also now be performed. We demonstrate a range of movement profiles for a variety of applications, in particular, lateral sliding wear. The developed NanoLAB TEM triboprobe also includes a new closed loop vision control system for intuitive control during positioning and alignment. It includes an automated online calibration to ensure that the fine piezotube is controlled accurately throughout any type of test. Both the 3D programmability and the closed loop vision feedback system are demonstrated here.

Invisible decays of the lightest Higgs boson in supersymmetric models

We consider supersymmetric models in which the lightest Higgs scalar can decay invisibly consistent with the constraints on the 126 GeV state discovered at the CERN LHC. We consider the invisible decay in the minimal supersymmetric standard model (MSSM), as well its extension containing an additional chiral singlet superfield, the so-called next-to-minimal or nonminimal supersymmetric standard model (NMSSM). We consider the case of MSSM with both universal as well as nonuniversal gaugino masses at the grand unified scale, and find that only an E-6 grand unified model with unnaturally large representation can give rise to sufficiently light neutralinos which can possibly lead to the invisible decay h(0) -> (chi) over tilde (0)(1)(chi) over tilde (0)(1). Following this, we consider the case of NMSSM in detail, where we also find that it is not possible to have the invisible decay of the lightest Higgs scalar with universal gaugino masses at the grand unified scale. We delineate the regions of the NMSSM parameter space where it is possible for the lightest Higgs boson to have a mass of about 126 GeV, and then concentrate on the region where this Higgs can decay into light neutralinos, with the soft gaugino masses M-1 and M-2 as two independent parameters, unconstrained by grand unification. We also consider, simultaneously, the other important invisible Higgs decay channel in the NMSSM, namely the decay into the lightest CP-odd scalars, h(1) -> a(1)a(1), which is studied in detail. With the invisible Higgs branching ratio being constrained by the present LHC results, we find that mu(eff) < 170 GeV and M-1 < 80 GeV are disfavored in NMSSM for fixed values of the other input parameters. The dependence of our results on the parameters of NMSSM is discussed in detail.

Espectáculos cortesanos en la América española del siglo XVII : las fiestas como caso para el análisis de la relación entre la Corte y la Corte virreinal

La Corte madrileña de los Austrias, al igual que el resto de las monarquías europeas del siglo XVII, generó una variada gama de fiestas públicas y privadas, como por ejemplo teatro musical, mascaradas y procesiones callejeras en las que desfilaban carros alegóricos con danzantes y músicos. Estos espectáculos no eran un mero entretenimiento sino que estaban destinados a resaltar las virtudes del monarca y a hacer conscientes a los espectadores del lugar que les cabía ocupar en esa sociedad recurriendo para ello a un complejo discurso simbólico. Las Cortes virreinales de América trasladaron a sus territorios estas prácticas que valían, fundamentalmente, para hacer presente la figura del rey y mantener viva la lealtad a la corona. Analizamos dos ejemplos de fiesta, una mascarada celebrada en Pausa (Perú) y un intermedio dramáticomusical en Sucre, que nos revelan la forma de pensamiento, las conductas y la organización de la sociedad cortesana virreinal.

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C₁₂ and C₁₈ alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.

Fuzzy inferring mathematical morphology and optical implementation

Fuzzification is introduced into gray-scale mathematical morphology by using two-input one-output fuzzy rule-based inference systems. The fuzzy inferring dilation or erosion is defined from the approximate reasoning of the two consequences of a dilation or an erosion and an extended rank-order operation. The fuzzy inference systems with numbers of rules and fuzzy membership functions are further reduced to a simple fuzzy system formulated by only an exponential two-input one-output function. Such a one-function fuzzy inference system is able to approach complex fuzzy inference systems by using two specified parameters within it-a proportion to characterize the fuzzy degree and an exponent to depict the nonlinearity in the inferring. The proposed fuzzy inferring morphological operators tend to keep the object details comparable to the structuring element and to smooth the conventional morphological operations. Based on digital area coding of a gray-scale image, incoherently optical correlation for neighboring connection, and optical thresholding for rank-order operations, a fuzzy inference system can be realized optically in parallel. (C) 1996 Society of Photo-Optical Instrumentation Engineers.

I. The effect of N,N,N',N' -tetramethylethylenediamine on the Schlenk Equilibrium. II. The nature of the Di-Grignard reagent

I. The influence of N,N,N’,N’-tetramethylethylenediamine on the Schlenk equilibrium

The equilibrium between ethylmagnesium bromide, diethylmagnesium, and magnesium bromide has been studied by nuclear magnetic resonance spectroscopy. The interconversion of the species is very fast on the nmr time scale, and only an averaged spectrum is observed for the ethyl species. When N,N,N’,N’-tetramethylethylenediamine is added to solutions of these reagents in tetrahydrofuran, the rate of interconversion is reduced. At temperatures near -50°, two ethylmagnesium species have been observed. These are attributed to the different ethyl groups in ethylmagnesium bromide and diethylmagnesium, two of the species involved in the Schlenk equilibrium of Grignard reagents.

II. The nature of di-Grignard reagents

Di-Grignard reagents have been examined by nuclear magnetic resonance spectroscopy in an attempt to prove that dialkylmagnesium reagents are in equilibrium with alkylmagnesium halides. The di-Grignard reagents of compounds such as 1,4-dibromobutane have been investigated. The dialkylmagnesium form of this di-Grignard reagent can exist as an intramolecular cyclic species, tetramethylene-magnesium. This cyclic form would give an nmr spectrum different from that of the classical alkylmagnesium halide di-Grignard reagent. In dimethyl ether-tetrahydrofuran solutions of di-Grignard reagents containing N N,N,N’,N’-Tetramethylethylenediamine, evidence has been found for the existence of an intramolecular dialkylmagnesium species. This species is rapidly equilibrating with other forms, but at low temperatures, the rates of interconversion are reduced. Two species can be seen in the nmr spectrum at -50°. One is the cyclic species; the other is an open form.

Inversion of the carbon at the carbon-magnesium bond in di-Grignard reagents has also been studied. This process is much faster than in corresponding monofunctional Grignard reagents.

Adesão e sobrevida de pacientes em um programa de assistência medicamentosa para doença de Alzheimer no Rio de Janeiro: um estudo baseado em relacionamento de bases de dados

A doença de Alzheimer (DA) afeta mais de um milhão de habitantes no Brasil com grande impacto tanto na saúde como social e financeiro. O uso adequado de medicamentos e os programas de cuidado integrado são recomendados como as melhores práticas nesta doença. Em 2002, o Ministério da Saúde criou o Programa de Assistência Farmacêutica aos Portadores de doença de Alzheimer que garante aos portadores desta patologia acesso à avaliação por especialistas e tratamento medicamentoso de alto custo. Mas, para um melhor planejamento das ações relacionadas ao programa, é importante entender os padrões de morbi-mortalidade da população alvo, qualidade da assistência oferecida e o seu impacto. Com foco nesse cenário, esta tese teve como objetivo o estudo da adesão, mortalidade e sobrevida em uma população portadora de doença de Alzheimer assistida nesse programa de assistência farmacêutica. Para apresentação dessa pesquisa, dividiram-se os resultados em três artigos. No primeiro artigo, o objetivo foi avaliar a viabilidade de se utilizar as informações de reabastecimento de receitas coletadas por esse programa na construção de medidas de adesão, uma metodologia já explorada na literatura internacional, mas com experiência limitada no Brasil. Os dados foram acessados nos formulários de Autorização de Procedimentos de Alto Custo (APAC) armazenados na base de dados do programa de acesso de medicamentos excepcionais do Sistema de Informação Ambulatorial (SIA). Como resultado, foram criadas várias medidas de adesão com potencial aplicação no campo da farmacoepidemiologia e planejamento em saúde. No segundo artigo, o foco foi entender que fatores individuais, terapêuticos ou relacionados à assistência, poderiam estar relacionados com um aumento do risco de abandono do programa. Fatores como o sexo feminino, o número de comorbidades na APAC, o tipo de inibidor de colinesterase iniciado e a irregularidade nos reabastecimentos foram associados a um maior risco de abandono do programa. No terceiro artigo, pelas técnicas de relacionamento probabilístico de base de dados, agregaram-se os dados presentes no Sistema de Informação sobre Mortalidade (SIM) para avaliação dos padrões de mortalidade desta patologia. Cerca de 40% dos pacientes foram a óbito durante todo o período de seguimento e principal causa básica de mortalidade foi a doença de Alzheimer (19%). Idade mais avançada e sexo masculino foram as únicas variáveis associadas com uma menor sobrevida. A persistência no programa em seis meses e os diferentes níveis de adesão, medidos pela proporção de posse da medicação, não mostraram associação com a sobrevida. Conclui-se que os dados disponíveis nas bases possibilitaram a investigação do padrão de mortalidade e utilização de um programa de assistência na doença de Alzheimer. E, a possibilidade de analisar grandes populações, em caráter contínuo, com medidas objetivas e com um custo relativamente baixo suplanta o caráter limitado das informações individuais e da doença. Políticas que suportem o aumento na disponibilidade, qualidade e escopo da informação e o avanço nas metodologias de pesquisa em bases de dados devem ser uma prioridade da saúde, pois contribuem com a criação de informações relevantes para um uso racional de recursos e melhora nas práticas de cuidado.

Entre a tiramnya cruel e a pedra fundamental: a obrigatoriedade do ensino primário como uma técnica de governo de Minas Gerais

Os discursos políticos educacionais acerca da institucionalização da instrução elementar em Minas Gerais atravessaram todo o século XIX, apontando também como uma preocupação republicana, ora pelo discurso de impraticabilidade e ferimento aos direitos civis, ora pela defesa de seu caráter estatal e da argumentação de função civilizatória e disciplinar da população. Nesse sentido, pensar a compulsoriedade do ensino demanda uma compreensão da sua função social, o conhecimento dos agentes envolvidos e de seus interesses sobre tal medida de governo. De acordo com os defensores da obrigatoriedade do ensino no século XIX e início do XX, o intuito da educação seria formar cidadãos civilizados e instruídos. Tal perspectiva estava relacionada a um projeto de sociedade e de nação brasileira, para o qual era imprescindível formar, desde a infância, um povo disciplinado, um povo bem governado. O nosso objetivo foi analisar o tema da obrigatoriedade do ensino a partir do conceito foucaultiano de governamentalidade. Problematizando a ideia de que universalizar o acesso à educação representava apenas uma iniciativa de garantia de direitos, a hipótese que defendemos consiste na ideia de que o ensino obrigatório pode ter sido perspectivado enquanto uma estratégia de governo dos outros, de controle dos sujeitos. Partindo desse pressuposto, como efeito esperado, seria possível obter sujeito com outras atitudes, as atitudes derivadas da coação promovida pela escola. Ao legitimar a escola, o dispositivo da obrigatoriedade funcionaria como estratégia e produziria positividades. Por meio da escola e de seu caráter compulsório, tratava-se de atingir e gerir a população dos pequenos, de modo a equipá-la com os códigos mínimos do mundo civilizado, com os efeitos disciplinares correlatos.Para tanto, analisamos a legislação de Minas Gerais, impressos mineiros (Correio de Minas, Jornal do Commercio, Minas Livre, O Granbery) e a bibliografia acerca da obrigatoriedade da instrução primária, a fim de identificar traços do debate no Império e na passagem para a República, os quais foram problematizados à luz daquele conceito. A partir dessa discussão, concluímos que a obrigatoriedade do ensino é mais bem compreendida se analisada em outro registro que não seja meramente jurídico. Tal inferência aponta para a ampliação do quadro analítico acerca dessa política compulsória e dos interesses de Estado em torno dela.

ReefBase 2.0: a contribution to environmental conservation on a global scale

The 1997 International Year of the Reef sees the release of ReefBase 2.0: a global database on coral reefs and their resources. It provides the most comprehensive and accessible repository of information to date. Containing information on over 7000 coral reefs in more than 123 countries, ReefBase 2.0 offers an extensive range of time-related data pertaining to coastal tourism, benthic environment ecology, fish population statistics, oceanography, socioeconomics, mariculture, and harvest activities. It also outlines the stresses causing reef degradation as well as management initiatives. Complemented by hundreds of digitized maps provided by the World Conservation Monitoring Centre (WCMC) and over 500 high quality photographs, ReefBase 2.0 is not only an essential tool for coral reef management but also an comprehensive guide for tourists, scuba divers and snorkelers alike. ReefBase has contributed substantially to the success of the International Coral Reef Institute (ICRI) and serves as the official database of the Global Coral Reef Monitoring Network (GCRMN), bringing together an increasing volume of data on coral reef health, management and significance to humanity, and making it widely available. Over the next five years, the information contained within ReefBase will be utilized as an instrument for developing coral reef health assessment criteria, sustainable management criteria, and providing continuously updated summaries of threats endangering coral reefs around the globe. This will be a strong basis for focused corrective action in an attempt to conserve coral reefs and properly manage their resources for future generations.

Compostagem de Resíduos Agroextrativistas no Município de Laranjal do Jari - Amapá.

Esta dissertação tem como objetivo, a apresentação de uma proposta para os resíduos agroextrativistas a fim de encontrar um composto orgânico ideal para ser utilizado na agricultura do Município de Laranjal do Jari, no Estado do Amapá. A técnica em questão será a compostagem, gerando uma alternativa de utilização para os resíduos de natureza local, onde atualmente não vêm sendo aproveitados. Para se chegar ao composto ideal serão utilizados basicamente: caroços de açaí e cascas de castanha. Esses resíduos vêm sendo relegados através dos Serviços de Limpeza Pública, constituindo não só um problema estético ou ambiental, mas de desperdício de energia e materiais que poderiam ser utilizados na recuperação de áreas degradadas ou como composto orgânico, na fixação de nutrientes e água no solo a fim de melhorar as práticas agrícolas, reduzir custos e a importação de fertilizantes químicos. A metodologia envolve estudo bibliográfico sobre a técnica de compostagem, consistindo em desenvolver todas as etapas que se darão mais claras, no desenvolver dos trabalhos de campo, para uma futura implantação de uma Unidade de Compostagem, a ser aplicável para a agricultura do referido município.

Reserved parking : marine reserves and small-scale fishing communities: a collection of articles from SAMUDRA report

As the earth’s resources continue to face increasing pressure from a variety of human and natural causes, protection of the environment and biodiversity is a matter of contemporary concern, The conservation of coastal and marine resources, in particular, has become a priority for countries around the world. In this context, marine protected areas (MPAs) are being widely promoted as one of the most effective tools for the conservation of coastal and marine resources. Most MPAs are located in coastal areas of great biodiversity, and hence their development has direct impacts on the lives and livelihoods of coastal communities, especially small-scale and traditional fishing communities. Typically, they are the ones who have to bear the costs of conservation practices–lost livelihood options, expulsion from traditional fishing grounds and living spaces, and violation of human/community rights, to name a few. The articles in this dossier, drawn chronologically from the pages of Samudra Report, the triannual publication of ICSF, draw attention to these issues. They show that conservation and livelihoods are closely intertwined, and that top-down, non-participatory models of conservation can be counter-productive. Despite being poor and powerless, fishing and coastal communities can be powerful allies in conservation efforts, given their longstanding dependence on natural resources and their traditional ecological knowledge systems. As the examples in this dossier reveal, it is possible for fishing communities to protect and conserve the environment, while continuing with sustainable fishing operations. Clearly, only an integrated approach to fisheries management and conservation will prove successful. This dossier will be useful for policymakers, social scientists, non-governmental organizations and others interested in fisheries, conservation, communities and livelihoods.

Plastic limit solution for the response of plate anchors under combined translational and torsional undrained loading

Plate anchors are increasingly being used to moor large floating offshore structures in deep and ultradeep water. These facilities impart substantial vertical uplift loading to plate anchors. However, extreme operating conditions such as hurricane loading often result in partial system failures, with significant change in the orientation of the remaining intact mooring lines. The purpose of this study is to investigate the undrained pure translational (parallel to plate) and torsional bearing capacity of anchor plates idealized as square and rectangular shaped plates. Moreover, the interaction response of plate anchors under combined translational and torsional loading is studied using a modified plastic limit analysis (PLA) approach. The previous PLA formulation which did not account for shear-normal force interaction on the vertical end faces of the plate provides an exact solution to the idealized problem of an infinitely thin plate but only an approximate solution to the problem of a plate of finite thickness. This is also confirmed by the three-dimensional finite element (FE) results, since the PLA values exceed FE results as the thickness of the plate increases. By incorporating the shear-normal interaction relationship in the modified solution, the torsional bearing capacity factors, as well as the plate interaction responses are enhanced as they show satisfactory agreement with the FE results. The interaction relationship is then obtained for square and rectangular plates of different aspect ratios and thicknesses. The new interaction relationships could also be used as an associated plastic failure locus for combined shear and torsional loading to predict plastic displacements and rotations in translational and torsional loading modes as well. Copyright © 2011 by the International Society of Offshore and Polar Engineers (ISOPE).