Functional model for catecholase-like activity: A mechanistic approach with manganese(III) complexes of salen type Schiff base ligands

Three new Mn(III) complexes [MnL1(OOCH)(OH2)] (1), [MnL2(OH2)(2)][Mn2L22(NO2)(3)] (2) and [Mn2L21(NO2)(2)] (3) (where H2L1 = H(2)Me(2)Salen = 2,7-bis(2-hydroxyphenyl)-2,6-diazaocta-2,6-diene and H2L2 = H(2)Salpn = 1,7-bis(2-hydroxyphenyl)-2,6-diazahepta-1,6-diene) have been synthesized. X-ray crystal structure analysis reveals that 1 is a mononuclear species whereas 2 contains a mononuclear cationic and a dinuclear nitrite bridged (mu-1 kappa O:2 kappa O') anionic unit. Complex 3 is a phenoxido bridged dimer containing terminally coordinated nitrite. Complexes 1-3 show excellent catecholase-like activity with 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. Kinetic measurements suggest that the rate of catechol oxidation follows saturation kinetics with respect to the substrate and first order kinetics with respect to the catalyst. Formation of bis(mu-oxo)dimanganese(III,III) as an intermediate during the course of reaction is identified from ESI-MS spectra. The characteristic six line EPR spectra of complex 2 in the presence of 3,5-DTBC supports the formation of manganese(II)-semiquinonate as an intermediate species during the catalytic oxidation of 3,5-DTBC.

Estimates of aerosol radiative forcing from the MACC re-analysis

The European Centre for Medium-range Weather Forecast (ECMWF) provides an aerosol re-analysis starting from year 2003 for the Monitoring Atmospheric Composition and Climate (MACC) project. The re-analysis assimilates total aerosol optical depth retrieved by the Moderate Resolution Imaging Spectroradiometer (MODIS) to correct for model departures from observed aerosols. The reanalysis therefore combines satellite retrievals with the full spatial coverage of a numerical model. Re-analysed products are used here to estimate the shortwave direct and first indirect radiative forcing of anthropogenic aerosols over the period 2003–2010, using methods previously applied to satellite retrievals of aerosols and clouds. The best estimate of globally-averaged, all-sky direct radiative forcing is −0.7±0.3Wm−2. The standard deviation is obtained by a Monte-Carlo analysis of uncertainties, which accounts for uncertainties in the aerosol anthropogenic fraction, aerosol absorption, and cloudy-sky effects. Further accounting for differences between the present-day natural and pre-industrial aerosols provides a direct radiative forcing estimate of −0.4±0.3Wm−2. The best estimate of globally-averaged, all-sky first indirect radiative forcing is −0.6±0.4Wm−2. Its standard deviation accounts for uncertainties in the aerosol anthropogenic fraction, and in cloud albedo and cloud droplet number concentration susceptibilities to aerosol changes. The distribution of first indirect radiative forcing is asymmetric and is bounded by −0.1 and −2.0Wm−2. In order to decrease uncertainty ranges, better observational constraints on aerosol absorption and sensitivity of cloud droplet number concentrations to aerosol changes are required.

Impact of the modal aerosol scheme GLOMAP-mode on aerosol forcing in the Hadley Centre Global Environmental Model

The Hadley Centre Global Environmental Model (HadGEM) includes two aerosol schemes: the Coupled Large-scale Aerosol Simulator for Studies in Climate (CLASSIC), and the new Global Model of Aerosol Processes (GLOMAP-mode). GLOMAP-mode is a modal aerosol microphysics scheme that simulates not only aerosol mass but also aerosol number, represents internally-mixed particles, and includes aerosol microphysical processes such as nucleation. In this study, both schemes provide hindcast simulations of natural and anthropogenic aerosol species for the period 2000–2006. HadGEM simulations of the aerosol optical depth using GLOMAP-mode compare better than CLASSIC against a data-assimilated aerosol re-analysis and aerosol ground-based observations. Because of differences in wet deposition rates, GLOMAP-mode sulphate aerosol residence time is two days longer than CLASSIC sulphate aerosols, whereas black carbon residence time is much shorter. As a result, CLASSIC underestimates aerosol optical depths in continental regions of the Northern Hemisphere and likely overestimates absorption in remote regions. Aerosol direct and first indirect radiative forcings are computed from simulations of aerosols with emissions for the year 1850 and 2000. In 1850, GLOMAP-mode predicts lower aerosol optical depths and higher cloud droplet number concentrations than CLASSIC. Consequently, simulated clouds are much less susceptible to natural and anthropogenic aerosol changes when the microphysical scheme is used. In particular, the response of cloud condensation nuclei to an increase in dimethyl sulphide emissions becomes a factor of four smaller. The combined effect of different 1850 baselines, residence times, and abilities to affect cloud droplet number, leads to substantial differences in the aerosol forcings simulated by the two schemes. GLOMAP-mode finds a presentday direct aerosol forcing of −0.49Wm−2 on a global average, 72% stronger than the corresponding forcing from CLASSIC. This difference is compensated by changes in first indirect aerosol forcing: the forcing of −1.17Wm−2 obtained with GLOMAP-mode is 20% weaker than with CLASSIC. Results suggest that mass-based schemes such as CLASSIC lack the necessary sophistication to provide realistic input to aerosol-cloud interaction schemes. Furthermore, the importance of the 1850 baseline highlights how model skill in predicting present-day aerosol does not guarantee reliable forcing estimates. Those findings suggest that the more complex representation of aerosol processes in microphysical schemes improves the fidelity of simulated aerosol forcings.

Transmission of wireless power by magnetic resonance

The work involves investigation of a type of wireless power system wherein its analysis will yield the construction of a prototype modeled as a singular technological artifact. It is through exploration of the artifact that forms the intellectual basis for not only its prototypical forms, but suggestive of variant forms not yet discovered. Through the process it is greatly clarified the role of the artifact, its most suitable application given the constraints on the delivery problem, and optimization strategies to improve it. In order to improve maturity and contribute to a body of knowledge, this document proposes research utilizing mid-field region, efficient inductive-transfer for the purposes of removing wired connections and electrical contacts. While the description seems enough to state the purpose of this work, it does not convey the compromises of having to redraw the lines of demarcation between near and far-field in the traditional method of broadcasting. Two striking scenarios are addressed in this thesis: Firstly, the mathematical explanation of wireless power is due to J.C. Maxwell's original equations, secondly, the behavior of wireless power in the circuit is due to Joseph Larmor's fundamental works on the dynamics of the field concept. A model of propagation will be presented which matches observations in experiments. A modified model of the dipole will be presented to address the phenomena observed in the theory and experiments. Two distinct sets of experiments will test the concept of single and two coupled-modes. In a more esoteric context of the zero and first-order magnetic field, the suggestion of a third coupled-mode is presented. Through the remaking of wireless power in this context, it is the intention of the author to show the reader that those things lost to history, bound to a path of complete obscurity, are once again innovative and useful ideas.

Spontaneous local symmetry breaking: a conformational study of glycine on Cu{311}

Understanding the interplay between intrinsic molecular chirality and chirality of the bonding footprint is crucial in exploiting enantioselectivity at surfaces. As such, achiral glycine and chiral alanine are the most obvious candidates if one is to study this interplay on different surfaces. Here, we have investigated the adsorption of glycine on Cu{311} using reflection-absorption infrared spectroscopy, low-energy electron diffraction, temperature-programmed desorption and first-principles density-functional theory. This combination of techniques has allowed us to accurately identify the molecular conformations present under different conditions, and discuss the overlayer structure in the context of the possible bonding footprints. We have observed coverage-dependent local symmetry breaking, with three-point bonded glycinate moieties forming an achiral arrangement at low coverages, and chirality developing with the presence of two-point bonded moieties at high coverages. Comparison with previous work on the self-assembly of simple amino acids on Cu{311} and the structurally-similar Cu{110} surface has allowed us to rationalise the different conditions necessary for the formation of ordered chiral overlayers.

Individual differences in early language learning: a study of English learners of French

The present longitudinal study examines the interaction of learner variables (gender, motivation, self-efficacy and first language literacy) and their influence on second language learning outcomes. The study follows English learners of French from Year 5 in primary school (aged 9-10) to the first year in secondary school (Year 7 aged 11-12). Language outcomes were measured by two oral production tasks; a sentence repetition task and a photo description task both of which were administered at three time points. Longitudinal data on learner attitudes and motivation were collected via questionnaires. Teacher assessment data for general first language literacy attainment were also provided. The results show a great deal of variation in learner attitudes and outcomes and that there is a complex relationship between first language literacy, self-efficacy, gender and attainment. For example, in general, girls held more positive attitudes to boys and were more successful. However, the inclusion of first language ability, which explained 30-40% of variation, shows that gender differences in attitudes and outcomes are likely mediated by first language literacy and prior learning experience.

Optimal infinity-quasiconformal immersions

For a Hamiltonian K ∈ C2(RN × n) and a map u:Ω ⊆ Rn − → RN, we consider the supremal functional (1) The “Euler−Lagrange” PDE associated to (1)is the quasilinear system (2) Here KP is the derivative and [ KP ] ⊥ is the projection on its nullspace. (1)and (2)are the fundamental objects of vector-valued Calculus of Variations in L∞ and first arose in recent work of the author [N. Katzourakis, J. Differ. Eqs. 253 (2012) 2123–2139; Commun. Partial Differ. Eqs. 39 (2014) 2091–2124]. Herein we apply our results to Geometric Analysis by choosing as K the dilation function which measures the deviation of u from being conformal. Our main result is that appropriately defined minimisers of (1)solve (2). Hence, PDE methods can be used to study optimised quasiconformal maps. Nonconvexity of K and appearance of interfaces where [ KP ] ⊥ is discontinuous cause extra difficulties. When n = N, this approach has previously been followed by Capogna−Raich ? and relates to Teichmüller’s theory. In particular, we disprove a conjecture appearing therein.

Digital image correlation analysis of the load transfer by implant-supported restorations

This study compared splinted and non-splinted implant-supported prosthesis with and without a distal proximal contact using a digital image correlation method. An epoxy resin model was made with acrylic resin replicas of a mandibular first premolar and second molar and with threaded implants replacing the second premolar and first molar. Splinted and non-splinted metal-ceramic screw-retained crowns were fabricated and loaded with and without the presence of the second molar. A single-camera measuring system was used to record the in-plane deformation on the model surface at a frequency of 1.0 Hz under a load from 0 to 250 N. The images were then analyzed with specialist software to determine the direct (horizontal) and shear strains along the model. Not splinting the crowns resulted in higher stress transfer to the supporting implants when the second molar replica was absent. The presence of a second molar and an effective interproximal contact contributed to lower stress transfer to the supporting structures even for non-splinted restorations. Shear strains were higher in the region between the molars when the second molar was absent, regardless of splinting. The opposite was found for the region between the implants, which had higher shear strain values when the second molar was present. When an effective distal contact is absent, non-splinted implant-supported restorations introduce higher direct strains to the supporting structures under loading. Shear strains appear to be dependent also on the region within the model, with different regions showing different trends in strain changes in the absence of an effective distal contact. (C) 2011 Elsevier Ltd. All rights reserved.

Interleukin-10 attenuates vascular responses to endothelin-1 via effects on ERK1/2-dependent pathway

Giachini FR, Zemse SM, Carneiro FS, Lima VV, Carneiro ZN, Callera GE, Ergul A, Webb RC, Tostes RC. Interleukin-10 attenuates vascular responses to endothelin-1 via effects on ERK1/2-dependent pathway. Am J Physiol Heart Circ Physiol 296: H489-H496, 2009. First published December 12, 2008; doi:10.1152/ajpheart.00251.2008.-Interleukin-10 (IL-10) is an anti-inflammatory cytokine with protective actions on the vasculature. On the other hand, endothelin ( ET)-1 has potent vasoconstrictor, mitogenic, and proinflammatory activities, which have been implicated in the pathophysiology of a number of cardiovascular diseases. We hypothesized that, in a condition where ET-1 expression is upregulated, i.e., on infusion of TNF-alpha, IL-10 confers vascular protection from ET-1-induced injury. Aortic rings and first-order mesenteric arteries from male C57BL/6 (WT) and IL-10-knockout (IL-10(-/-)) mice were treated with human recombinant TNF-alpha (220 ng.kg(-1).day(-1)) or vehicle (saline) for 14 days. TNF-alpha infusion significantly increased blood pressure in IL-10(-/-), but not WT, mice. TNF-alpha augmented vascular ET-1 mRNA expression in arteries from WT and IL-10(-/-) mice. ET type A (ETA) receptor expression was increased in arteries from IL-10(-/-) mice, and TNF-alpha infusion did not change vascular ETA receptor expression in control or IL-10(-/-) mice. Aorta and mesenteric arteries from TNF-alpha-infused IL-10(-/-) mice displayed increased contractile responses to ET-1, but not the ET type B receptor agonist IRL-1620. The ETA receptor antagonist atrasentan completely abolished responses to ET-1 in aorta and mesenteric vessels, whereas the ERK1/2 inhibitor PD-98059 abrogated increased contractions to ET-1 in arteries from TNF-alpha-infused IL-10(-/-) mice. Infusion of TNF-alpha, as well as knockdown of IL-10 (IL-10(-/-)), induced an increase in total and phosphorylated ERK1/2. These data demonstrate that IL-10 counteracts ET(A)-mediated vascular responses to ET-1, as well as activation of the ERK1/2 pathway.

Under flow impedimetric measurements using magnetic particles for label-free detection affinity target

The necessity to adapt sensors based on electrochemical techniques for high throughput analysis control increases the interest to develop new analytical systems able to perform measurements under buffer now. In this report we explored the possibility of employing a new system to make impedimetric measurements to detect the interaction between proteins and small molecules. The well-known biotin-streptavidin interaction was adopted to evaluate the proposed assembly. This system allows us to perform experiments under flow. Magnetic beads functionalized with streptavidin were used and first characterized using AFM and FTIR. Non-faradic impedance spectroscopy allowed the detection of the biotin-streptavidin interaction. Using our new system and under a flow of PBS buffer, 5 10-5 M of biotin was detected with a stable signal. (c) 2007 Elsevier B.V. All rights reserved.

Handling Equality in Monodic Temporal Resolution

First-order temporal logic is a concise and powerful notation, with many potential applications in both Computer Science and Artificial Intelligence. While the full logic is highly complex, recent work on monodic first-order temporal logics has identified important enumerable and even decidable fragments including the guarded fragment with equality. In this paper, we specialise the monodic resolution method to the guarded monodic fragment with equality and first-order temporal logic over expanding domains. We introduce novel resolution calculi that can be applied to formulae in the normal form associated with the clausal resolution method, and state correctness and completeness results.

Exclusão social: gestão estratégica de pessoas em duas subsidiárias de uma empresa multinacional

The present study of case empirically investigates the existence of indicators that suggest the social exclusion preoccupation from the organizations with a strategic management of human resources focus. The objects of study are two subsidiaries of a multinational enterprise in emergency and first-aid services area. One of them is Portuguese and the other is a Brazilian one. This exploratory research has used a sectional way with a longitudinal perspective, since it has considered a specific verified data referring to 2004 and 2005 years, beyond the deeper interviews with actual managers to an evaluation of these studied perception and its authentication. Our indicators identification sources were principally the individual and social rights and duties broaching and the fundamental guarantees disposed in the Brazilian and Portuguese Constitutions as such as the European Constitution project. The results appoint to great differences of management between both subsidiaries, being the Brazilian one closer to our research proposes, as such as suggest us that the human resource areas, still acting in an instrumentalist way, establish a great barrier to better practices in social inclusion and they would be unprepared for a management with the focus in the employees. Although our study has been realized in a specific activity enterprise, we believe that our results can stimulate the realization of other investigations with the same objectives. In this way, we contribute to a better comprehension of the social exclusion causes and the organizations participations in this process.

Transexualismo: as decisões do Poder Judiciário no tocante à alteração do prenome a partir da Carta Cidadã de 1988

À luz do instituído pela Constituição Federal de 1988, os direitos fundamentais passaram a ser vistos sob um novo olhar. Todavia, temas considerados complexos, como o transexualismo, segundo a Classificação Internacional das Doenças (CID 10) considerado “Transtorno de Identidade Sexual”, ainda suscitam maior aprofundamento por parte da sociedade, do poder judiciário e do poderes executivo e legislativo. O Sistema Único de Saúde – SUS passou a permitir a cirurgia de transgenitalização no Brasil, na qual se opera a redesignação de sexo, tendo sido estipulados por lei critérios para a sua realização. Após a cirurgia, surge um problema: o da identidade civil, uma vez que o novo gênero da pessoa operada não se coaduna com o seu registro civil, causando-lhe constrangimento. Não há lei que regule a matéria. A partir desta constatação, o presente estudo se propõe a explorar as decisões judiciais de todos os estados da Federação, por intermédio de pesquisa nos sites dos seus respectivos tribunais, bem como das cortes superiores, buscando os termos “transexual” e “prenome” e utilizando o filtro temporal a partir de 1988, ano da promulgação da Carta Cidadã, até final de 2010. Tendo em vista a falta de lei que normatize a matéria, o escopo primordial consiste na obtenção de uma narrativa de como vêm sendo decididas as demandas na temática ora proposta. A conclusão do trabalho sugere que apesar de não haver um marco normativo estabelecido, o discurso do poder judiciário se utiliza de diversos argumentos de ordem social, psicológica e jurídica, devidamente sistematizados e apreciados, bem como de princípios jurídicos, sendo, nesse caso, o princípio da dignidade da pessoa humana, previsto na Carta Magna, o mais utilizado.

The Olympic impact on hosting candidate countries

In this paper, we analyze the impact of hosting the Summer Olympics on macroeconomic aggregates such as GDP, consumption, government consumption and investments per capita. The data is in panel structure and includes the period of ten years before and ten years after the event containing the Olympic Summer Games between 1960 and 1996. The sample countries comprise only candidates to host the games. This sampling strategy allows us to estimate the average treatment effect consistently, because it is assumed that these countries are comparable to each other, including those that ultimately hosted the games. The impact of hosting the Olympic games is measured by Fixed Effect and First Difference regressions. Moreover, we do a structural break test developed by Andrews (1993) to identify if hosting the Olympic Games creates anticipation effects for demand changes that stimulate current GDP, consumption, government consumption and investments. The results indicate a positive effect of the Summer Olympics in all variables of interest. However, the distribution in time and anticipation of these effects is unclear in the tests, changing significantly depending on the model and the significance level used.

Programa de Promoção da Igualdade de Oportunidade para Todos: experiências de ação afirmativa do Ministério Público do Trabalho (2003-2012)

Nos últimos anos o Brasil tem avançado no sentido de enfrentar as desigualdades raciais. Em 1995, o então Presidente da República Fernando Henrique Cardoso reconheceu oficial e publicamente não apenas a existência da discriminação racial e do preconceito de cor no País, mas também a necessidade de se adotar medidas públicas e privadas para fazer face ao problema. Naquele mesmo ano foi criado o Grupo de Trabalho Interministerial, que teve por incumbência propor ações integradas de combate à discriminação racial e recomendar políticas para a consolidação da cidadania da população negra. Para encaminhar as ações relacionadas ao mercado de trabalho, foi criado em 1996, no âmbito do Ministério do Trabalho, o Grupo de Trabalho para a Eliminação da Discriminação no Emprego e na Ocupação, cuja missão foi definir programas de ações que visassem ao combate da discriminação no emprego e na ocupação. Desde então, temos presenciado uma maior permeabilidade do Estado às demandas e proposições dos movimentos sociais negros. Marcos nesta trajetória foram a criação da SEPPIR – Secretaria de Promoção da Igualdade racial, em 2003, a aprovação do Estatuto da Igualdade Racial, em 2010, e a aprovação, por unanimidade, do sistema de cotas para negros no ensino superior brasileiro, pelo Superior Tribunal Federal, em 2011. Essas, dentre outras, são conquistas inquestionáveis e que revelam que o País vive um período de inflexão no encaminhamento de soluções para os problemas raciais que o assolam. Mas, se por um lado essas conquistas representam grandes vitórias, especialmente quando analisadas sob uma perspectiva retroativa, visto que desde a abolição da escravatura nenhuma ação estatal havia sido direcionada à solução de desigualdades raciais, por outro, muito ainda temos que avançar. Um olhar prospectivo revelará que o fosso criado ao longo desses séculos não poderia ser superado em apenas 20 anos. Muita desigualdade racial ainda resta. E muito ainda resta a ser feito para o seu enfrentamento. Ao “mobilizar conhecimento para a resolução de problemas sociais relevantes” (FARAH, 2012) esta tese busca contribuir para o avanço das políticas de igualdade racial no País, particularmente daquelas voltadas para o mercado de trabalho. Ela se constitui em um estudo de caso do Programa de Promoção da Igualdade de Oportunidade para Todos, uma iniciativa do Ministério Público do Trabalho, que teve por objetivo levar as organizações privadas a adotar ações afirmativas para o enfrentamento das desigualdades de gênero e raça nas relações de trabalho. Para a condução do estudo de caso único, empreendemos uma pesquisa qualitativa, adotando diversas técnicas de pesquisa, como a observação participante, conversas, entrevistas semiestruturadas e análise de documentos e outras materialidades, tendo o pós-construcionismo como sua perspectiva epistemológica (SPINK, 2005). Analisamos o Programa da Promoção da Igualdade de Oportunidade para Todos a partir das seguintes variáveis: sua concepção, implantação e primeiros resultados. Essa análise conduziu-nos a uma revisão da literatura nacional e estrangeira sobre a gestão da diversidade, e da literatura sobre desigualdade categórica durável. Os resultados deste estudo sugerem que, em que pesem as resistências enfrentadas para a sua implantação, o Programa já produziu efeitos positivos, embora também apontem seus limites e ajustes necessários para futuras políticas que visem à redução de desigualdade racial no mercado de trabalho no País.