Computational and experimental study of the behavior of cyano-based ionic liquids in aqueous solution

The solvation of cyano- (CN-) based ionic liquids (ILs) and their capacity to establish hydrogen bonds (H-bonds) with water was studied by means of experimental and computational approaches. Experimentally, water activity data were measured for aqueous solutions of ILs based on 1-butyl-3-methylimidazolium ([BMIM](+)) cation combined with one of the following anions: thiocyanate ([SCN](-)), dicyanamide ([DCA](-)), or tricyanomethanide ([TCM](-)), and of 1-ethyl-3-methylimidazolium tetracyanoborate ([EMIM][TCB]). From the latter data, water activity coefficients were estimated showing that [BMIM][SCN] and [BMIM][DCA], unlike [BMIM][TCM] and [EMIM][TCB], are able to establish favorable interactions with water. Computationally, the conductor like screening model for real solvents (COSMO-RS) was used to estimate the water activity coefficients which compare well with the experimental ones. From the COSMO-RS results, it is suggested that the polarity of each ion composing the ILs has a strong effect on the solvation phenomena. Furthermore, classical molecular dynamics (MD) simulations were performed for obtaining an atomic level picture of the local molecular neighborhood of the different species. From the experimental and computational data it is showed that increasing the number of CN groups in the ILs' anions does not enhance their ability to establish H-bonds with water but decreases their polarities, being [BMIM][DCA] and [BMIM][SCN] the ones presenting higher propensity to interact.

The Effect of Private Management of Public Schools on Student Achievement in Bogotá, Colombia

During the last 15 years, the public school system in Bogotá, Colombia has maintained a concession system in which 25 schools are managed privately with exemptions to many of the rules required in the traditional schools -- This study uses the propensity score matching technique to examine whether students in the privately-managed schools have better scores on the Saber 11° examinations taken upon completion of secondary school -- The results for 251 schools indicates that students with comparable socioeconomic characteristics score considerably better on these tests in the privately-managed schools than in the traditional public schools -- Thus, there is evidence that the privately-managed public schools are a cost-effective alternative to the traditional public school

Banca Digital

Em plena quarta revolução industrial, todas as industrias se estão a transformar para se ajustar aos novos paradigmas de relação com os clientes, altamente influenciados pelos pioneiros digitais como a Uber, Netflix ou Amazon, porém no setor financeiro há desafios acrescidos, pois os clientes esperam juntar essas expectativas digitais com a manutenção da iteração humana, enquanto, do lados bancos, em simultâneo, necessitam de recuperar da crise da dívida soberana que impôs necessidades de ajustamento dos balanços. O momento de desenvolvimento tecnológico potenciado pelo forte crescimento do acesso à internet em mobilidade traz novos hábitos e expectativas na relação com as entidades, com dispositivos cada vez mais potentes a cada vez menor custo, o que criou a oportunidade perfeita para o surgimento de startups tecnológicas dispostas a transformar os modelos de negócio de intermediação clássica, dando origem, no setor financeiro, às fintechs – empresas de base tecnológica dedicadas à prestação de serviços financeiros - impondo uma disrupção na industria financeira, com destaque para mercados como os EUA e Reino Unido. Olhando aos últimos cinco anos do setor financeiro, será muito difícil antecipar como estará o setor financeiro dentro de cinco anos, mas sabemos que estará seguramente muito diferente do que conhecemos hoje, por esse fato este trabalho é assente essencialmente em referências bibliográficas dos últimos 5 anos, tendo sido feito utilizados estudos de investigação de empresas e documentos académicos para a caracterização do setor neste contexto de inovação permanente e em que medida este processo de “digitalização” do setor financeiro influencia a propensão dos clientes na contratação de mais produtos e serviços, sendo esse um fator central para os bancos em Portugal recuperarem economicamente. É também analisada a dimensão seguida pelas instituições de regulação e supervisão do setor financeiro com vista a potenciar a concorrência e inovação do setor financeiro, enquanto mantém a garantia de segurança, confiança e controlo de risco sistémico. É bastante escassa a literatura disponível para caracterizar a banca em Portugal numa ótica de inovação e transformação, porém este trabalho procura caracterizar o sistema financeiro português face à forma como está a responder aos desafios de transformação tecnológica e digital. Procurou-se estabelecer uma metodologia de investigação que permita caracterizar a perceção de valor acrescentado para os clientes da utilização de serviços digitais e em que medida estes se podem substituir aos balcões e à intervenção humana dos profissionais dos bancos, tendo-se concluído que estes dois elementos são ainda fatores centrais para os clientes.

The Cambridge Equation with government activity revisited

Neste artigo faz-se uma análise das características distributivas do processo Kaldor-Pasinetti, assumindo-se que o setor governamental incorre em persistentes déficits que podem ser financiados através de diferentes instrumentos, como a emissão de títulos e de moeda. Através dessa abordagem é possível estudar como a atividade governamental afeta a distribuição de renda entre capitalistas e trabalhadores e assim obter generalizações do Teorema de Cambridge em que versões anteriores como as de Steedman (1972), Pasinetti (1989), Dalziel (1991) e Faria (2000) surgem como casos particulares. _________________________________________________________________________________ ABSTRACT

Don’t expect me to vote for you just because I like you, even if you do make me feel warm inside: a comparison of the validity of non-ipsative measures of party support

The inclusion of non-ipsative measures of party preference (in essence ratings for each of the parties of a political system) has become established practice in mass surveys conducted for election studies. They exist in different forms, known as thermometer ratings or feeling scores, likes and dislikes scores, or support propensities. Usually only one of these is included in a single survey, which makes it difficult to assess the relative merits of each. The questionnaire of the Irish National Election Study 2002 (INES2002) contained three different batteries of non-ipsative party preferences. This paper investigates some of the properties of these different indicators. We focus in particular on two phenomena. First, the relationship between non-ipsative preferences and the choices actually made on the ballot. In Ireland this relationship is more revealing than in most other countries owing to the electoral system (STV) which allows voters to cast multiple ordered votes for candidates from different parties. Second, we investigate the latent structure of each of the batteries of party preferences and the relationships between them. We conclude that the three instruments are not interchangeable, that they measure different orientations, and that one –the propensity to vote for a party– is by far preferable if the purpose of the study is the explanation of voters’ actual choice behaviour. This finding has important ramifications for the design of election study questionnaires.

Associações entre a potência muscular dos membros inferiores e a saúde óssea avaliada através de ultrassonografia quantitativa

Objetivo: Analisar as associações entre a potência muscular dos membros inferiores e a saúde óssea avaliada através de ultrassonografia quantitativa. Métodos: A amostra incluiu 63 crianças de 9 anos de idade. A velocidade de som (VS) do rádio e da tíbia foi avaliada através de ultrassonografia quantitativa, a potência de salto foi estimada a partir de um salto vertical com contramovimento e a maturidade somática foi determinada a partir da estimação do pico de velocidade em altura. O estado geral de saúde e o historial de fraturas foram avaliados através de questionário. As associações entre medidas dos parâmetros ósseos e a potência de salto foram analisadas através de correlações bivariadas, com as variáveis expressas em valores absolutos e relativos (estandardizados). Resultados: Foram observadas associações positivas entre a maturidade somática e a potência de salto expressa tanto em valores absolutos como relativos (p <0,05). A maturidade somática correlacionou-se ainda positivamente com a VS da tíbia nas raparigas (r=0,358, p=0,045), enquanto nos rapazes se verificou uma associação negativa, embora não significativa (r=-0,290, p=0,126). Observou-se uma associação ou propensão para associação negativa entre a VS da tíbia e a potência de salto nos rapazes (r=-0,490, p=0,007) e nas raparigas (r=-0,344, p=0,054). Conclusão: A potência de salto não parece constituir um bom marcador da saúde óssea de rapazes e raparigas de 9 anos de idade quando avaliada através de ultrassom.

Structural characterization and comparative analysis of human and piscine cartilage acidic protein (CRTAC1/CRTAC2)

Dissertação de mestrado, Biotecnologia, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2014

Implementação de um modelo de erosão para a simulação de carreiras dos Oficiais da Marinha Portuguesa

Em outubro de 2012, a Direção de Análise e Gestão da Informação (DAGI), em colaboração com a Superintendência do Pessoal (SP) e Direção do Pessoal (DP), iniciou o desenvolvimento de um protótipo de simulador, que designou por “Protótipo Fluxo de Carreiras”. Este simulador permite parametrizar diversos fatores que condicionam o desenvolvimento de carreira dos militares e que estão associados a mecanismos reguladores de carreira que se encontram vertidos no Estatuto dos Militares das Forças Armadas (EMFAR). Para cada ano do período de simulação, a situação de cada militar de uma determinada classe é atualizada e são verificadas as condições para a ocorrência de promoções e passagens à reserva. O evento “passagem à reserva” de um militar pode ter origem em regras determinísticas (exemplo: militar atinge a idade limite de passagem à reserva no seu posto) ou em condições estocásticas ou aleatórias (exemplos: óbito, exclusão da promoção, requerer voluntariamente a passagem à reserva, etc.). Estas últimas situações resultam do fenómeno de erosão dos quadros que pode ser observado a partir do histórico de saídas desta natureza. Até 2015, o simulador de carreiras não comtemplava um modelo de erosão, pelo que os resultados disponibilizados (indicadores de fluxo de carreira) dependiam exclusivamente de mecanismos determinísticos. Desta forma estes resultados apresentam uma natureza “pessimista” e com fraca aderência à realidade. O presente trabalho tem como objetivo construir um modelo descritivo da erosãodos militares oficiais da Marinha, tendo por base dados de saídas (excetuando saídas relacionadas com regras determinísticas previstas no EMFAR) no período de 2008 a2015. Para cada classe da categoria de oficiais é estimada uma função de probabilidadecondicional ao tempo de serviço efetivo ou à idade do militar que representa apropensão para um militar sair do quadro antes de ser verificada uma condição determinística. Estas funções foram integradas no simulador de carreiras para que os resultados possam reproduzir a componente de erosão. Usando o método de simulação de Monte Carlo é possível obter a distribuição dos indicadores de fluxo de carreira. Porfim, objetiva-se realizar uma comparação entre uma simulação com fatores estocásticos (com erosão) e uma simulação considerando apenas fatores determinísticos (semerosão). Este trabalho visa refletir o panorama atual da erosão de pessoal na Marinha, permitindo assim melhorar a qualidade das previsões de efetivos ao longo do tempo bem como aumentar a capacidade de intervenção e resposta na identificação e correção antecipada de possíveis estruturações.

Três ensaios sobre avaliação de políticas públicas para o estado de Goiás

Tese (doutorado)—Universidade de Brasília, Departamento de Economia, Brasília, 2016.

Effets des variations dans l’implantation d’un programme sur le risque cardiométabolique dans six CSSS de Montréal sur les résultats chez les patients

En 2011, l’Agence de la santé et des services sociaux de Montréal (ASSSM), en partenariat avec les Centres de santé et services sociaux (CSSS) de la région, a coordonné la mise en œuvre d’un programme de prévention et de prise en charge intégré sur le risque cardiométabolique. Ce programme, s’inspirant du Chronic Care Model et s’adressant aux patients atteints de diabète et d’hypertension artérielle, est d’une durée de deux ans et comporte une séquence de suivis individuels avec l’infirmière et la nutritionniste, de cours de groupe et de séances d’activité physique. L’objectif de ce mémoire est d’évaluer, à l’aide d’un devis quasi-expérimental, l’impact de la variation dans l’implantation de certains aspects du programme dans les six CSSS participant à l’étude sur les résultats de santé des patients. Cinq aspects du programme ont été retenus : les ressources, la conformité au processus clinique prévu dans le programme régional, la maturité du programme, la coordination interne au sein de l’équipe de soins et la coordination externe avec les médecins de 1re ligne. Des analyses de différence de différences, incluant des scores de propension afin de rendre les groupes comparables, ont été effectuées dans le but d’évaluer l’influence de ces aspects sur quatre indicateurs de santé : l’hémoglobine glyquée, l’atteinte de la cible de tension artérielle et l’atteinte de deux cibles d’habitudes de vie concernant la répartition des glucides alimentaires et la pratique d’activité physique. Les résultats indiquent que les indicateurs de santé sélectionnés se sont améliorés chez les patients participant au programme et ce, indépendamment des variations dans son implantation entre les CSSS participant à l’étude. Très peu d’analyses de différence de différences ont en effet relevé un impact significatif des variables d’implantation étudiées sur ces indicateurs. Les résultats suggèrent que les effets bénéfiques d’un tel programme sont davantage tributaires de la prestation des interventions auprès des patients que d’aspects organisationnels liés à son implantation.

Comparaison populationnelle des résultats périopératoires entre la néphro-urétérectomie ouverte et laparoscopique aux États-Unis

Introduction : La néphro-urétérectomie radicale (NUR) représente le traitement primaire pour les patients atteints d’une tumeur des voies excrétrices supérieures (TVES) non métastatique. Une approche ouverte ou laparoscopique peut être considérée. Malgré la présence de plusieurs études comparant les résultats périopératoires et oncologiques entre ces deux approches, aucunes études se basent sur une cohorte populationnelle. Objectif : Notre but est d’évaluer la morbidité péri-opératoire entre la NUR ouverte et laparoscopique en utilisant une cohorte populationnelle. Méthode : Nous avons utilisé la base de donnée Nationwide Inpatient Sample (NIS) pour identifier tous les patients atteints d’une TVES non métastatique, traités par NUR ouverte ou laparoscopique, entre 1998 et 2009. Au total, 7401 (90,8%) et 754 (9,2%) patients ont subi une NUR ouverte et laparoscopique, respectivement. Dans le but de contrôler les différences inhérentes entre les deux groupes, nous avons utilisé une analyse par appariement sur les scores de propension. Ainsi, 3016 (80%) patients avec NUR ouverte étaient appariés à 754 (20%) patients avec NUR laparoscopique. Intervention : Tous les patients ont subi une NUR. Mesures : Les taux de complications intra-opératoires et post-opératoires, de transfusions sanguines, d’hospitalisation prolongée et de mortalité intrahospitalière ont été mesurés. Des analyses de régression logistique on été utilisées pour notre cohorte, après appariement sur les scores de propension. Résultats et Limitations : Pour les patients traités par approche ouverte vs. laparoscopique, les taux suivants furent calculés : transfusions sanguines : 15 vs. 10% (p<0,001); complications intra-opératoires : 4,7 vs. 2,1% (p=0,002); complications post-opératoires : 17 vs. 15% (p=0,24); durée d’hospitalisation prolongée (≥ 5 jours) : 47 vs. 28% (p<0,001); mortalité intra-hospitalière 1,3 vs. 0,7% (p=0,12). Sur les analyses par régression logistique, les patients ayant été traités par NUR laparoscopique avaient moins de chance de recevoir une transfusion sanguine (odds ratio [OR]: 0,6, p<0,001), de subir une complication intra-opératoire (OR: 0,4, p=0,002), et d’avoir une durée prolongée d’hospitalisation (OR: 0,4, p<0,001). Globalement les taux de complications postopératoires étaient équivalents. Toutefois, l’approche laparoscopique était associée à moins de complications pulmonaires (OR: 0,4, p=0,007). Cette étude est limitée par sa nature rétrospective. Conclusion: Après ajustement de potentiels biais de sélection, la NUR par approche laparoscopique est associée à moins de complications intraopératoires et péri-opératoires comparée à la NUR par approche ouverte.

L’évaluation des déterminants des paramètres hémodynamiques centraux à l’aide de la cohorte populationnelle CARTaGENE.

Les maladies cardiovasculaires ont un impact considérable sur la vie des Canadiens, et de nombreux efforts ont permis d’identifier différents facteurs de risque associés à cette condition. L’hypertension artérielle représente un de ces facteurs modifiables les plus importants. Quoique l’hypertension est définie à l’aide de mesures de pression artérielle en périphérie, il devient de plus en plus apparent que la mesure de pression centrale et de ses composantes auraient des avantages au niveau de la prédiction de la survenue d’événements cardiovasculaires. Le présent mémoire vise à mieux caractériser deux déterminants de cette pression centrale, le traitement antihypertenseur à base de bêtabloqueurs et l’insuffisance rénale chronique précoce. En utilisant les données recueillies dans la banque de données populationnelle CARTaGENE, il a été possible à l’aide d’analyses statistiques par appariement basé sur le coefficient de propension de démontrer que l’utilisation d’agents antihypertensifs de type bêtabloqueurs était associée à un profil hémodynamique central défavorable. Ainsi, les individus recevant ces agents avaient une pression centrale et une amplification artérielle plus élevées que des individus du groupe contrôle apparié et ce, malgré une pression périphérique identique. Cet effet semblait être incomplètement expliqué par la réduction du rythme cardiaque associé à l’utilisation de bêtabloqueurs. Aussi, il a été démontré que l’insuffisance rénale chronique de stade 3 (débit de filtration glomérulaire estimé entre 30 et 60 mL/min/1.73m2) n’était pas associée à une élévation des paramètres hémodynamiques centraux, contrairement à ce qui avait déjà été décrit chez des individus avec insuffisance rénale chronique plus avancée. De plus, le niveau d’albuminurie ne serait également pas associé à un changement du profil central dans un sous-groupe de la cohorte CARTaGENE.

What Determines the Innovativeness of Polish Family Firms? Empirical Results and Theoretical Puzzles

This article will review and synthesize the existing research on the innovativeness of Polish family firms in order to separate universal factors that influence the degree of innovativeness of firms from the factors which distinctively influence the innovativeness of family firms. To better assess the innovation propensity of family firms the author will work out the typology by combining the variety of innovations with particular features of family firms and the industrial context. A more nuanced approach will help to understand why the academic literature is inconclusive with regards to the question of whether family firms are anti-innovative (as some authors claim), pro-innovative or ambivalent with regard to innovations. In particular it will be argued that when assessing family firms’ innovativeness special attention needs to be paid to the impact of the management of intergenerational change on the propensity to innovate, as this process relates to the capacity for investments into innovativeness and the time horizon of the owner’s decisions.

GENETIC VARIATION, LOCAL ADAPTATION AND POPULATION STRUCTURE IN NORTH AMERICAN RED OAK SPECIES, QUERCUS RUBRA L. AND Q. ELLIPSOIDALIS E. J. HILL

Forest trees, like oaks, rely on high levels of genetic variation to adapt to varying environmental conditions. Thus, genetic variation and its distribution are important for the long-term survival and adaptability of oak populations. Climate change is projected to lead to increased drought and fire events as well as a northward migration of tree species, including oaks. Additionally, decline in oak regeneration has become increasingly concerning since it may lead to decreased gene flow and increased inbreeding levels. This will in turn lead to lowered levels of genetic diversity, negatively affecting the growth and survival of populations. At the same time, populations at the species’ distribution edge, like those in this study, could possess important stores of genetic diversity and adaptive potential, while also being vulnerable to climatic or anthropogenic changes. A survey of the level and distribution of genetic variation and identification of potentially adaptive genes is needed since adaptive genetic variation is essential for their long-term survival. Oaks possess a remarkable characteristic in that they maintain their species identity and specific environmental adaptations despite their propensity to hybridize. Thus, in the face of interspecific gene flow, some areas of the genome remain differentiated due to selection. This characteristic allows the study of local environmental adaptation through genetic variation analyses. Furthermore, using genic markers with known putative functions makes it possible to link those differentiated markers to potential adaptive traits (e.g., flowering time, drought stress tolerance). Demographic processes like gene flow and genetic drift also play an important role in how genes (including adaptive genes) are maintained or spread. These processes are influenced by disturbances, both natural and anthropogenic. An examination of how genetic variation is geographically distributed can display how these genetic processes and geographical disturbances influence genetic variation patterns. For example, the spatial clustering of closely related trees could promote inbreeding with associated negative effects (inbreeding depression), if gene flow is limited. In turn this can have negative consequences for a species’ ability to adapt to changing environmental conditions. In contrast, interspecific hybridization may also allow the transfer of genes between species that increase their adaptive potential in a changing environment. I have studied the ecologically divergent, interfertile red oaks, Quercus rubra and Q. ellipsoidalis, to identify genes with potential roles in adaptation to abiotic stress through traits such as drought tolerance and flowering time, and to assess the level and distribution of genetic variation. I found evidence for moderate gene flow between the two species and low interspecific genetic differences at most genetic markers (Lind and Gailing 2013). However, the screening of genic markers with potential roles in phenology and drought tolerance led to the identification of a CONSTANS-like (COL) gene, a candidate gene for flowering time and growth. This marker, located in the coding region of the gene, was highly differentiated between the two species in multiple geographical areas, despite interspecific gene flow, and may play a role in reproductive isolation and adaptive divergence between the two species (Lind-Riehl et al. 2014). Since climate change could result in a northward migration of trees species like oaks, this gene could be important in maintaining species identity despite increased contact zones between species (e.g., increased gene flow). Finally I examined differences in spatial genetic structure (SGS) and genetic variation between species and populations subjected to different management strategies and natural disturbances. Diverse management activities combined with various natural disturbances as well as species specific life history traits influenced SGS patterns and inbreeding levels (Lind-Riehl and Gailing submitted).

Redox regulation of Ras proteins in Dictyostelium discoideum

Reactive oxygen species are a normal consequence of life in an aerobic environment. However when they deviate from the narrow permissible range in cells, oxidative damage can occur. Dictyostelium discoideum is a model organism ideal for the study of cell signaling events such as those affected by oxidative stress. It was previously shown that Ras signaling in Dictyostelium is affected by genetic inactivation of the antioxidant enzyme Superoxide dismutase C (SodC) and in vitro data suggests that the NKCD motif of Ras is the redox target of superoxide.^ The main objective of this project was to determine the mechanism of superoxide mediated Ras regulation in vivo. To accomplish the main objective, we cloned, and in some cases, mutated different Ras proteins and later determined their activity in wild type and sodC- cells. RasC and RasD showed normal activation in sodC- cells, however RasG and RasS displayed high Ras activity. These last two Ras proteins contain the NKC118D motif inside the nucleotide binding region. A mutation of cysteine 118 to alanine in RasG rendered the protein less active in sodC- than the wild type RasG protein and a mutation alanine118 to cysteine in RasD conferred redox sensitivity to this small GTPase. Additionally, the propensity of RasG to be targeted by superoxide was evident when the environment of wild type cells was manipulated to induce the internal generation of superoxide through changes in the extracellular ion levels mainly magnesium. Lack of magnesium ions increased the intracellular level of superoxide and severely hampered directional cell migration. Chemotaxis of cells expressing RasG was negatively impacted by the absence of magnesium ions; however rasG- cells did not seem to be affected in their ability to perform chemotaxis. The last experiment implies that RasG is an important mediator of cell signaling during oxidative stress, responsible for preventing cells from continuing their developmental program. Our study suggests that the cysteine residue in the NKCD motif is essential for mediating the redox sensitivity of Ras proteins in Dictyostelium and that RasG is an essential mediator of the response to oxidative stress in this organism.^