Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

Functional disability of adults in Brazil: prevalence and associated factors

ABSTRACT OBJECTIVE To estimate the prevalence and factors associated with functional disability in adults in Brazil. METHODS We used information from the health supplement of the National Household Sample Survey in 2008. The dependent variable was the functional disability among adults of 18 to 65 years, measured by the difficulty of walking about 100 meters; independent variables were: health plan membership, region of residence, state of domicile, education level, household income, economic activity, self-perception of health, hospitalization, chronic diseases, age group, sex, and color. We calculated the gross odds ratios (OR), and their respective confidence intervals (95%), and adjusted them for variables of study by ordinal logistic regression, following hierarchical model. Sample weights were considered in all calculations. RESULTS We included 18,745 subjects, 74.0% of whom were women. More than a third of adults reported having functional disability. The disability was significantly higher among men (OR = 1.17; 95%CI 1.09;1.27), people from 35 to 49 years (OR = 1.30; 95%CI 1.17;1.45) and 50 to 65 years (OR = 1.38; 95%CI 1.24;1.54); economically inactive individuals (OR = 2.21; 95%CI 1.65;2.96); adults who reported heart disease (OR = 1.13; 95%CI 1.03;1.24), diabetes mellitus (OR = 1.16; 95%CI 1.05;1.29), arterial systemic hypertension (OR = 1.10; 95%CI 1.02;1.18), and arthritis/rheumatism (OR = 1.24; 95%CI 1.15;1.34); and participants who were admitted in the last 12 months (OR = 2.35; 95%CI 1.73;3.2). CONCLUSIONS Functional disability is common among Brazilian adults. Hospitalization is the most strongly associated factor, followed by economic activity, and chronic diseases. Sex, age, education, and income are also associated. Results indicate specific targets for actions that address the main factors associated with functional disabilities and contribute to the projection of interventions for the improvement of the well-being and promotion of adults' quality of life.

Tetranuclear COPPER(II) complexes with macrocyclic and open-chain disiloxane ligands as catalyst precursors for hydrocarboxylation and oxidation of alkanes and 1-phenylethanol

Two new tetranuclear complexes [Cu-4(mu-O)(L-1)-Cl-4] and [Cu-4(mu(4)-O)(L-2)(2)Cl-4] (2), where H2L1 is a macrocyclic ligand resulting from [2+2] condensation of 2,6-diformy1-4-methylphanol (DFF) and 1,3-bis(aminopropy1)tetramethyldisiloxane, and HL2 is a 1:2 condensation product: of DFF with trimethylsilyl p-aminobenzoate, have been prepared. The structures of the products were established by Xray diffraction. The complexes have been characterised by FTIR, UV/Vis spectroscopy, ES1 mass-spectrometry and magnetic susceptibility measurements. The latter revealed that the letrftriuclear complexes can be descr bed as two ferromagnetically coupled dinuclear units, in which the two copper(II) ions interact antiferromacinetically. The ccimpi.iunds act as homogeneous catalyst precursors for a number of single-pot reactions, including (I) hydrocarbaxylation, with CO, H2O and K2S2O8, of a variety of linear and cyclic (n = 5-8) alkanes into the corresponding Cn+1 carboxylic acids, (ii) peroxidative oxidation of cyclohexane, and (iii) solvent-free microwave-assisted oxidation of 1-phenyletha.nol.

Meta-heuristics self-parameterization in a multi-agent scheduling system using case-based reasoning

This paper proposes a novel agent-based approach to Meta-Heuristics self-configuration. Meta-heuristics are algorithms with parameters which need to be set up as efficient as possible in order to unsure its performance. A learning module for self-parameterization of Meta-heuristics (MH) in a Multi-Agent System (MAS) for resolution of scheduling problems is proposed in this work. The learning module is based on Case-based Reasoning (CBR) and two different integration approaches are proposed. A computational study is made for comparing the two CBR integration perspectives. Finally, some conclusions are reached and future work outlined.

Severity of malocclusion in adolescents: populational-based study in the north of Minas Gerais, Brazil

ABSTRACT OBJECTIVE To identify the factors associated with severity of malocclusion in a population of adolescents. METHODS In this cross-sectional population-based study, the sample size (n = 761) was calculated considering a prevalence of malocclusion of 50.0%, with a 95% confidence level and a 5.0% precision level. The study adopted correction for the effect of delineation (deff = 2), and a 20.0% increase to offset losses and refusals. Multistage probability cluster sampling was adopted. Trained and calibrated professionals performed the intraoral examinations and interviews in households. The dependent variable (severity of malocclusion) was assessed using the Dental Aesthetic Index (DAI). The independent variables were grouped into five blocks: demographic characteristics, socioeconomic condition, use of dental services, health-related behavior and oral health subjective conditions. The ordinal logistic regression model was used to identify the factors associated with severity of malocclusion. RESULTS We interviewed and examined 736 adolescents (91.5% response rate), 69.9% of whom showed no abnormalities or slight malocclusion. Defined malocclusion was observed in 17.8% of the adolescents, being severe or very severe in 12.6%, with pressing or essential need of orthodontic treatment. The probabilities of greater severity of malocclusion were higher among adolescents who self-reported as black, indigenous, pardo or yellow, with lower per capita income, having harmful oral habits, negative perception of their appearance and perception of social relationship affected by oral health. CONCLUSIONS Severe or very severe malocclusion was more prevalent among socially disadvantaged adolescents, with reported harmful habits and perception of compromised esthetics and social relationships. Given that malocclusion can interfere with the self-esteem of adolescents, it is essential to improve public policy for the inclusion of orthodontic treatment among health care provided to this segment of the population, particularly among those of lower socioeconomic status.

Health self-assessment by hemodialysis patients in the Brazilian Unified Health System

ABSTRACT OBJECTIVE To examine whether the level of complexity of the services structure and sociodemographic and clinical characteristics of patients in hemodialysis are associated with the prevalence of poor health self-assessment. METHODS In this cross-sectional study, we evaluated 1,621 patients with chronic terminal kidney disease on hemodialysis accompanied in 81 dialysis services in the Brazilian Unified Health System in 2007. Sampling was performed by conglomerate in two stages and a structured questionnaire was applied to participants. Multilevel multiple logistic regression was used for data analysis. RESULTS The prevalence of poor health self-assessment was of 54.5%, and in multivariable analysis it was associated with the following variables: increasing age (OR = 1.02; 95%CI 1.01–1.02), separated or divorced marital status (OR = 0.62; 95%CI 0.34–0.88), having 12 years or more of study (OR = 0.51; 95%CI 0.37–0.71), spending more than 60 minutes in commuting between home and the dialysis service (OR = 1.80; 95%CI 1.29–2.51), having three or more self-referred diseases (OR = 2.20; 95%CI 1.33–3.62), and reporting some (OR = 2.17; 95%CI 1.66–2.84) or a lot of (OR = 2.74; 95%CI 2.04–3.68) trouble falling asleep. Individuals in treatment in dialysis services with the highest level of complexity in the structure presented less chance of performing a self-assessment of their health as bad (OR = 0.59; 95%CI 0.42–0.84). CONCLUSIONS We showed poor health self-assessment is associated with age, years of formal education, marital status, home commuting time to the dialysis service, number of self-referred diseases, report of trouble sleeping, and also with the level of complexity of the structure of health services. Acknowledging these factors can contribute to the development of strategies to improve the health of patients in hemodialysis in the Brazilian Unified Health System.

Smart Adhesive Joints: An overview of recent developments

Adhesive bonding is a viable technique for joining a wide range of materials. However, increasing the lifetime, reducing the costs, and improving the safety of structures are highly demanded nowadays. Hence, the development of new technologies and processes for easy recycle, heal, or self-heal of bonded structures are becoming of great interest for the industry. This paper provides an overview of the current developments in the use of “smart” adhesive technology and introduces the reader to early findings on the use of self-healing materials, thermally expandable particles, and nanoparticles, among others, in adhesives and their potential to increase the reliability of adhesive joints.

A director’s approach to art and religion : o quadro, um musical da Paixão segundo o sr. João (The masterpiece, a musical of The passion according to John): trabalho de projecto

Trabalho de Projecto submetido à Escola Superior de Teatro e Cinema para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Teatro - especialização em Encenação.

Generalization of Wertheim's theory for the assembly of various types of rings

We generalize Wertheim's first order perturbation theory to account for the effect in the thermodynamics of the self-assembly of rings characterized by two energy scales. The theory is applied to a lattice model of patchy particles and tested against Monte Carlo simulations on a fcc lattice. These particles have 2 patches of type A and 10 patches of type B, which may form bonds AA or AB that decrease the energy by epsilon(AA) and by epsilon(AB) = r epsilon(AA), respectively. The angle theta between the 2 A-patches on each particle is fixed at 601, 90 degrees or 120 degrees. For values of r below 1/2 and above a threshold r(th)(theta) the models exhibit a phase diagram with two critical points. Both theory and simulation predict that rth increases when theta decreases. We show that the mechanism that prevents phase separation for models with decreasing values of theta is related to the formation of loops containing AB bonds. Moreover, we show that by including the free energy of B-rings ( loops containing one AB bond), the theory describes the trends observed in the simulation results, but that for the lowest values of theta, the theoretical description deteriorates due to the increasing number of loops containing more than one AB bond.

Temperature-induced structural transitions in self-assembling magnetic nanocolloids

With the help of a unique combination of density functional theory and computer simulations, we discover two possible scenarios, depending on concentration, for the hierarchical self-assembly of magnetic nanoparticles on cooling. We show that typically considered low temperature clusters, i.e. defect-free chains and rings, merge into more complex branched structures through only three types of defects: four-way X junctions, three-way Y junctions and two-way Z junctions. Our accurate calculations reveal the predominance of weakly magnetically responsive rings cross-linked by X defects at the lowest temperatures. We thus provide a strategy to fine-tune magnetic and thermodynamic responses of magnetic nanocolloids to be used in medical and microfluidics applications.

Positive self-image over time

This paper incorporates egocentric comparisons into a human capital accumulation model and studies the evolution of positive self image over time. The paper shows that the process of human capital accumulation together with egocentric comparisons imply that positive self image of a cohort is first increasing and then decreasing over time. Additionally, the paper finds that positive self image: (1) peaks earlier in activities where skill depreciation is higher, (2) is smaller in activities where the distribution of income is more dispersed, (3) is not a stable characteristic of an individual, and (4) is higher for more patient individuals.

From Consciousness to Knowledge – The Explanatory Power of Revelation

Epistemology in philosophy of mind is a difficult endeavor. Those who believe that our phenomenal life is different from other domains suggest that self-knowledge about phenomenal properties is certain and therefore privileged. Usually, this so called privileged access is explained by the idea that we have direct access to our phenomenal life. This means, in contrast to perceptual knowledge, self-knowledge is non-inferential. It is widely believed that, this kind of directness involves two different senses: an epistemic sense and a metaphysical sense. Proponents of this view often claim that this is due to the fact that we are acquainted with our current experiences. The acquaintance thesis, therefore, is the backbone in justifying privileged access. Unfortunately the whole approach has a profound flaw. For the thesis to work, acquaintance has to be a genuine explanation. Since it is usually assumed that any knowledge relation between judgments and the corresponding objects are merely causal and contingent (e.g. in perception), the proponent of the privileged access view needs to show that acquaintance can do the job. In this thesis, however, I claim that the latter cannot be done. Based on considerations introduced by Levine, I conclude that this approach involves either the introduction of ontologically independent properties or a rather obscure knowledge relation. A proper explanation, however, cannot employ either of the two options. The acquaintance thesis is, therefore, bound to fail. Since the privileged access intuition seems to be vital to epistemology within the philosophy of mind, I will explore alternative justifications. After discussing a number of options, I will focus on the so called revelation thesis. This approach states that by simply having an experience with phenomenal properties, one is in the position to know the essence of those phenomenal properties. I will argue that, after finding a solution for the controversial essence claim, this thesis is a successful replacement explanation which maintains all the virtues of the acquaintance account without necessarily introducing ontologically independent properties or an obscure knowledge relation. The overall solution consists in qualifying the essence claim in the relevant sense, leaving us with an appropriate ontology for phenomenal properties. On the one hand, this avoids employing mysterious independent properties, since this ontological view is physicalist in nature. On the other hand, this approach has the right kind of structure to explain privileged self-knowledge of our phenomenal life. My final conclusion consists in the claim that the privileged access intuition is in fact veridical. It cannot, however, be justified by the popular acquaintance approach, but rather, is explainable by the controversial revelation thesis.

Productivity gains from migration: An analysis of Cape Verdean return migrants

Are return migrants more productive than non-migrants? If so, is it a causal effect or simply self-selection? Existing literature has not reached a consensus on the role of return migration for origin countries. To answer these research questions, an empirical analysis was performed based on household data collected in Cape Verde. One of the most common identification problems in the migration literature is the presence of migrant self-selection. In order to disentangle potential selection bias, we use instrumental variable estimation using variation provided by unemployment rates in migrant destination countries, which is compared with OLS and Nearest Neighbor Matching (NNM) methods. The results using the instrumental variable approach provide evidence of labour income gains due to return migration, while OLS underestimates the coefficient of interest. This bias points towards negative self-selection of return migrants on unobserved characteristics, although the different estimates cannot be distinguished statistically. Interestingly, migration duration and occupational changes after migration do not seem to influence post-migration income. There is weak evidence that return migrants from the United States have higher income gains caused by migration than the ones who returned from Portugal.

Synthesis and characterization of novel 4H-pyran-4-ylidene indole-based heterocyclic systems for several optical applications

The development of organic materials displaying high two-photon absorption (TPA) has attracted much attention in recent years due to a variety of potential applications in photonics and optoelectronics, such as three-dimensional optical data storage, fluorescence imaging, two-photon microscopy, optical limiting, microfabrication, photodynamic therapy, upconverted lasing, etc. The most frequently employed structural motifs for TPA materials are donor–pi bridge–acceptor (D–pi–A) dipoles, donor–pi bridge–donor (D–pi–D) and acceptor–pi bridge-acceptor (A–pi–A) quadrupoles, octupoles, etc. In this work we present the synthesis and photophysical characterization of quadrupolar heterocyclic systems with potential applications in materials and biological sciences as TPA chromophores. Indole is a versatile building block for the synthesis of heterocyclic systems for several optoelectronic applications (chemosensors, nonlinear optical, OLEDs) due to its photophysical properties and donor electron ability and 4H-pyran-4-ylidene fragment is frequently used for the synthesis of red light-emitting materials. On the other hand, 2-(2,6-dimethyl-4H-pyran-4-ylidene)malononitrile (1) and 1,3-diethyl-dihydro-5-(2,6-dimethyl-4H-pyran-4-ylidene)-2-thiobarbituric (2) units are usually used as strong acceptor moieties for the preparation of π-conjugated systems of the push-pull type. These building blocks were prepared by Knoevenagel condensation of the corresponding ketone precursor with malononitrile or 1,3-diethyl-dihydro-2-thiobarbituric acid. The new quadrupolar 4H-pyran-4-ylidene fluorophores (3) derived from indole were prepared through condensation of 5-methyl-1H-indole-3-carbaldehyde with the acceptor precursors 1 and 2, in the presence of a catalytical amount of piperidine. The new compounds were characterized by the usual spectroscopic techniques (UV-vis., FT-IR and multinuclear NMR - 1H, 13C).

The quantified-Self and wearable technologies in the workplace: implications and challenges for their implementations

Introduction of technologies in the workplace have led to a dramatic change. These changes have come with an increased capacity to gather data about one’s working performance (i.e. productivity), as well as the capacity to track one’s personal responses (i.e. emotional, physiological, etc.) to this changing workplace environment. This movement of self-monitoring or self-sensing using diverse types of wearable sensors combined with the use of computing has been identified as the Quantified-Self. Miniaturization of sensors, reduction in cost and a non-stop increase in the computer power capacity has led to a panacea of wearables and sensors to track and analyze all types of information. Utilized in the personal sphere to track information, a looming question remains, should employers use the information from the Quantified-Self to track their employees’ performance or well-being in the workplace and will this benefit employees? The aim of the present work is to layout the implications and challenges associated with the use of Quantified-Self information in the workplace. The Quantified-Self movement has enabled people to understand their personal life better by tracking multiple information and signals; such an approach could allow companies to gather knowledge on what drives productivity for their business and/or well-being of their employees. A discussion about the implications of this approach will cover 1) Monitoring health and well-being, 2) Oversight and safety, and 3) Mentoring and training. Challenges will address the question of 1) Privacy and Acceptability, 2) Scalability and 3) Creativity. Even though many questions remain regarding their use in the workplace, wearable technologies and Quantified-Self data in the workplace represent an exciting opportunity for the industry and health and safety practitioners who will be using them.