Calixarene and Resorcarene Based Receptors: From Structural and Thermodynamic Studies to the Synthesis of a New Mercury(II) Selective Material

Materials used in current technological approaches for the removal of mercury lack selectivity. Given that this is one of the main features of supramolecular chemistry, receptors based on calix[4]arene and calix[4]resorcarene containing functional groups able to interact selectively with polluting ions while discriminating against biologically essential ones were designed. Thus two receptors, a partially functionalized calix[4]arene derivative, namely, 5,11,17,23-tetra-tert-butyl [25-27-bis(diethyl thiophosphate amino)dihydroxy] calix[4]arene (1) and a fully functionalized calix[4]resorcarene, 4,6,10,12,16,18,22,24-diethyl thiophosphate calix[4]resorcarene (2) are introduced. Mercury(II) was the identified target due to the environmental and health problems associated with its presence in water Thus following the synthesis and characterization of 1 and 2 in solution ((1)HNMR) and in the solid state (X-ray crystallography) the sequence of experimental events leading to cation complexation studies in acetonitrile and methanol ((1)H NMR, conductance, potentiometric, and calorimetric measurements) with the aim of assessing their behavior as mercury selective receptors are described. The cation selectivity pattern observed in acetonitrile follows the sequence Hg(II) > Cu(II) > Ag(I). In methanol 1 is also selective for Hg(II) relative to Ag(I) but no interaction takes place between this receptor and Cu(II) in this solvent. Based on previous results and experimental facts shown in this paper, it is concluded that the complexation observed with Cu(II) in acetonitrile occurs through the acetonitrile-receptor adduct rather than through the free ligand. Receptor 2 has an enhanced capacity for uptaking Hg(II) but forms metalate complexes with Cu(II). These studies in solution guided the inmobilization of receptor 1 into a silica support to produce a new and recyclable material for the removal of Hg(II) from water. An assessment on its capacity to extract this cation from water relative to Cu(II) and Ag (I) shows that the cation selectivity pattern of the inmobilized receptor is the same as that observed for the free receptor in methanol. These findings demonstrate that fundamental studies play a critical role in the selection of the receptor to be attached to silicates as well as in the reaction medium used for the synthesis of the new decontaminating agent.

Statistical coupling analysis of aspartic proteinases based on crystal structures of the Trichoderma reesei enzyme and its complex with pepstatin A

The crystal structures of an aspartic proteinase from Trichoderma reesei (TrAsP) and of its complex with a competitive inhibitor, pepstatin A, were solved and refined to crystallographic R-factors of 17.9% (R(free)=21.2%) at 1.70 angstrom resolution and 15.81% (R(free) = 19.2%) at 1.85 angstrom resolution, respectively. The three-dimensional structure of TrAsP is similar to structures of other members of the pepsin-like family of aspartic proteinases. Each molecule is folded in a predominantly beta-sheet bilobal structure with the N-terminal and C-terminal domains of about the same size. Structural comparison of the native structure and the TrAsP-pepstatin complex reveals that the enzyme undergoes an induced-fit, rigid-body movement upon inhibitor binding, with the N-terminal and C-terminal lobes tightly enclosing the inhibitor. Upon recognition and binding of pepstatin A, amino acid residues of the enzyme active site form a number of short hydrogen bonds to the inhibitor that may play an important role in the mechanism of catalysis and inhibition. The structures of TrAsP were used as a template for performing statistical coupling analysis of the aspartic protease family. This approach permitted, for the first time, the identification of a network of structurally linked residues putatively mediating conformational changes relevant to the function of this family of enzymes. Statistical coupling analysis reveals coevolved continuous clusters of amino acid residues that extend from the active site into the hydrophobic cores of each of the two domains and include amino acid residues from the flap regions, highlighting the importance of these parts of the protein for its enzymatic activity. (C) 2008 Elsevier Ltd. All rights reserved.

Protocols between programs and proofs

In this paper we describe a new protocol that we call the Curry-Howard protocol between a theory and the programs extracted from it. This protocol leads to the expansion of the theory and the production of more powerful programs. The methodology we use for automatically extracting “correct” programs from proofs is a development of the well-known Curry-Howard process. Program extraction has been developed by many authors, but our presentation is ultimately aimed at a practical, usable system and has a number of novel features. These include 1. a very simple and natural mimicking of ordinary mathematical practice and likewise the use of established computer programs when we obtain programs from formal proofs, and 2. a conceptual distinction between programs on the one hand, and proofs of theorems that yield programs on the other. An implementation of our methodology is the Fred system. As an example of our protocol we describe a constructive proof of the well-known theorem that every graph of even parity can be decomposed into a list of disjoint cycles. Given such a graph as input, the extracted program produces a list of the (non-trivial) disjoint cycles as promised.

Assessing Merit Aid and Need-Based Aid At Private Institutions

Institutions provide students with full tuition merit awards through formal scholarship programs for outstanding performance in academics, leadership, community service, and athletics. This brief outlines how institutions fund and utilize merit to increase retention rates, particularly for minority and first generation students.

European business schools and global leadership: an examination of the admission criteria of the european master in management programs ranked by the Financial Times 2010

O aumento de empresas que operam internacionalmente requer o desenvolvimento de líderes mundiais para colocar as estratégias em prática. Embora este processo de desenvolvimento é importante para o mundo corporativo, muitos futuros executivos são graduados de escolas de administração de empresas que estão intimamente ligados ao mundo de negócios e, portanto, desempenhão um papel importante no processo. Esta pesquisa examina se os programas europeus “Master in Management” classificado pelo Financial Times em 2010 selecionam aqueles candidatos que são mais adequados para o desenvolvimento de liderança global. Portanto, três anteriores meta-estudos são sintetizados para produzir um perfil de competências classificadas de um líder global. Então, informações sobre os critérios de admissão dos programas de mestrado são coletadas e comparadas com este perfil. Os resultados mostram que seis competências são medidas por mais da metade dos programas: proficiência em Inglês, capacidade analítica (racionamento lógico e quantitativo), capacidade de comunicação, conhecimento do negócio global, determinação para alcançar, motivação e capacidade interpessoal. Além disso, as habilidades operacionais requerentes pelos líderes globais não são significativas no processo de admissão e o foco é sobre as habilidades analíticas. Comparação dos resultados com o perfil anteriormente desenvolvido abrangente indica que uma quantidade significativa de programas pode subestimar o significado de habilidades pessoais e características para o desenvolvimento de líderes globais.

Three essays on local demand for public services

Local provision of public services has the positive effect of increasing the efficiency because each locality has its idiosyncrasies that determine a particular demand for public services. This dissertation addresses different aspects of the local demand for public goods and services and their relationship with political incentives. The text is divided in three essays. The first essay aims to test the existence of yardstick competition in education spending using panel data from Brazilian municipalities. The essay estimates two-regime spatial Durbin models with time and spatial fixed effects using maximum likelihood, where the regimes represent different electoral and educational accountability institutional settings. First, it is investigated whether the lame duck incumbents tend to engage in less strategic interaction as a result of the impossibility of reelection, which lowers the incentives for them to signal their type (good or bad) to the voters by mimicking their neighbors’ expenditures. Additionally, it is evaluated whether the lack of electorate support faced by the minority governments causes the incumbents to mimic the neighbors’ spending to a greater extent to increase their odds of reelection. Next, the essay estimates the effects of the institutional change introduced by the disclosure on April 2007 of the Basic Education Development Index (known as IDEB) and its goals on the strategic interaction at the municipality level. This institutional change potentially increased the incentives for incumbents to follow the national best practices in an attempt to signal their type to voters, thus reducing the importance of local information spillover. The same model is also tested using school inputs that are believed to improve students’ performance in place of education spending. The results show evidence for yardstick competition in education spending. Spatial auto-correlation is lower among the lame ducks and higher among the incumbents with minority support (a smaller vote margin). In addition, the institutional change introduced by the IDEB reduced the spatial interaction in education spending and input-setting, thus diminishing the importance of local information spillover. The second essay investigates the role played by the geographic distance between the poor and non-poor in the local demand for income redistribution. In particular, the study provides an empirical test of the geographically limited altruism model proposed in Pauly (1973), incorporating the possibility of participation costs associated with the provision of transfers (Van de Wale, 1998). First, the discussion is motivated by allowing for an “iceberg cost” of participation in the programs for the poor individuals in Pauly’s original model. Next, using data from the 2000 Brazilian Census and a panel of municipalities based on the National Household Sample Survey (PNAD) from 2001 to 2007, all the distance-related explanatory variables indicate that an increased proximity between poor and non-poor is associated with better targeting of the programs (demand for redistribution). For instance, a 1-hour increase in the time spent commuting by the poor reduces the targeting by 3.158 percentage points. This result is similar to that of Ashworth, Heyndels and Smolders (2002) but is definitely not due to the program leakages. To empirically disentangle participation costs and spatially restricted altruism effects, an additional test is conducted using unique panel data based on the 2004 and 2006 PNAD, which assess the number of benefits and the average benefit value received by beneficiaries. The estimates suggest that both cost and altruism play important roles in targeting determination in Brazil, and thus, in the determination of the demand for redistribution. Lastly, the results indicate that ‘size matters’; i.e., the budget for redistribution has a positive impact on targeting. The third essay aims to empirically test the validity of the median voter model for the Brazilian case. Information on municipalities are obtained from the Population Census and the Brazilian Supreme Electoral Court for the year 2000. First, the median voter demand for local public services is estimated. The bundles of services offered by reelection candidates are identified as the expenditures realized during incumbents’ first term in office. The assumption of perfect information of candidates concerning the median demand is relaxed and a weaker hypothesis, of rational expectation, is imposed. Thus, incumbents make mistakes about the median demand that are referred to as misperception errors. Thus, at a given point in time, incumbents can provide a bundle (given by the amount of expenditures per capita) that differs from median voter’s demand for public services by a multiplicative error term, which is included in the residuals of the demand equation. Next, it is estimated the impact of the module of this misperception error on the electoral performance of incumbents using a selection models. The result suggests that the median voter model is valid for the case of Brazilian municipalities.

Trust-based trade

There is substantially more trade within national borders than across borders. An important explanation for this fact is the weak enforcement of international contracts. We develop a model in which agents build reputations to overcome this institutional failure. The model describes the interplay between institutional quality, reputations and the dynamics of international trade. It also rationalizes several empirical regularities. We find that history matters for trade volumes, but that its effects vary with the institutional setting of the country. The same is true for the efticacy of trade liberalization programs. Moreover, while stricter enforcement of contracts enhances trade in the short run, it makes it harder for individual traders to develop good reputations. We show that this indirect negative effect may produce an "institutional trap": for sufliciently low initial levels of contract enforcement, a small tightening in enforcement reduces future trade fiows. We find also that search frictions aggravate the problems created by weak enforceability of contracts, even if they impose no direct cost on agents. The model allows extensions in several directions. We outline two of them, indicating how one could study transnational networks and the effects of firm heterogeneity within our structure.

Impact of worksite health-promotion programs in hospital admission costs and medical leaves in a sample of brazilian companies

Programas de saúde e bem-estar têm sido adotados por empresas como forma de melhorar a saúde de empregados, e muitos estudos descrevem retornos econômicos positivos sobre os investimentos envolvidos. Entretanto, estudos mais recentes com metodologia melhor têm demonstrado retornos menores. O objetivo deste estudo foi investigar se características de programas de saúde e bem-estar agem como preditores de custos de internação hospitalar (em Reais correntes) e da proporção de funcionários que têm licença médica, entre Abril de 2014 e Maio de 2015, em uma amostra não-aleatória de empresas no Brasil, através de parceria com uma empresa gestora de ‘big data’ para saúde. Um questionário sobre características de programas de saúde no ambiente de trabalho foi respondida por seis grandes empresas brasileiras. Dados retirados destes seis questionários (presença e idade de programa de saúde, suas características – inclusão de atividades de screening, educação sobre saúde, ligação com outros programas da empresa, integração do programa à estrutura da empresa, e ambientes de trabalho voltado para a saúde – e a adoção de incentivos financeiros para aderência de funcionários ao programa), bem como dados individuais de idade, gênero e categoria de plano de saúde de cada empregado , foram usados para construir um banco de dados com mais de 76.000 indivíduos. Através de um modelo de regressão múltipla e seleção ‘stepwise’ de variáveis, a idade do empregado foi positivamente associada e a idade do programa de saúde e a categoria ‘premium’ de plano de saúde do funcionário foram negativamente associadas aos custos de internação hospitalar (como esperado). Inesperadamente, a inclusão de programas de screening e iniciativas de educação de saúde nos programas de saúde e bem-estar nas empresas foram identificados como preditores positivos significativos para custos de admissão hospitalar. Para evitar a inclusão errônea de licenças-maternidade, apenas os dados de licença médica de pacientes do sexo masculino foram analisados (dados disponíveis apenas para duas entre as companhias incluídas, com um total de 18.957 pacientes do sexo masculino). Analisando estes dados através de um teste Z para comparação de proporções, a empresa com programa de saúde que inclui atividades voltadas a cessação de hábitos ruins (como tabagismo e etilismo), controle de diabetes e hipertensão, e que adota incentivos financeiros para a aderência de funcionários ao programa tem menor proporção de empregados com licençca médica no período analisado, quando comparada com a outra empresa que não tem estas características (também conforme esperado). Entretanto, a companhia com menor proporção de funcionários com licença médica também foi aquela que adota programa de screening entre as atividades de seu programa de saúde. Potenciais fontes de ameaça à validade interna e externa destes resultados são discutidas, bem como possíveis explicações para a associação entre programas de screening e educação médica a piores indicadores de saúde nesta amostra de companhias são discutidas. Novos estudos com melhor desenho, com amostras maiores e randômicas são necessários para validar estes resultados e possivelmente melhorar a validade interna e externa destes resultados.

Assessing global economic activity linkages: an empirical exercise based on global autoregressive regression

Economic performance increasingly relies on global economic environment due to the growing importance of trade and nancial links among countries. Literature on growth spillovers shows various gains obtained by this interaction. This work aims at analyzing the possible e ects of a potential economic growth downturn in China, Germany and United States on the growth of other economies. We use global autoregressive regression approach to assess interdependence among countries. Two types of phenomena are simulated. The rst one is a one time shock that hit these economies. Our simulations use a large shock of -2.5 standard deviations, a gure very similar to what we saw back in the 2008 crises. The second experiment simulate the e ect of a hypothetical downturn of the aforementioned economies. Our results suggest that the United States play the role of a global economy a ecting countries across the globe whereas Germany and China play a regional role.

JML- Based formal development of a Java card application for managing medical appointments

Although formal methods can dramatically increase the quality of software systems, they have not widely been adopted in software industry. Many software companies have the perception that formal methods are not cost-effective cause they are plenty of mathematical symbols that are difficult for non-experts to assimilate. The Java Modelling Language (short for JML) Section 3.3 is an academic initiative towards the development of a common formal specification language for Java programs, and the implementation of tools to check program correctness. This master thesis work shows how JML based formal methods can be used to formally develop a privacy sensitive Java application. This is a smart card application for managing medical appointments. The application is named HealthCard. We follow the software development strategy introduced by João Pestana, presented in Section 3.4. Our work influenced the development of this strategy by providing hands-on insight on challenges related to development of a privacy sensitive application in Java. Pestana’s strategy is based on a three-step evolution strategy of software specifications, from informal ones, through semiformal ones, to JML formal specifications. We further prove that this strategy can be automated by implementing a tool that generates JML formal specifications from a welldefined subset of informal software specifications. Hence, our work proves that JML-based formal methods techniques are cost-effective, and that they can be made popular in software industry. Although formal methods are not popular in many software development companies, we endeavour to integrate formal methods to general software practices. We hope our work can contribute to a better acceptance of mathematical based formalisms and tools used by software engineers. The structure of this document is as follows. In Section 2, we describe the preliminaries of this thesis work. We make an introduction to the application for managing medical applications we have implemented. We also describe the technologies used in the development of the application. This section further illustrates the Java Card Remote Method Invocation communication model used in the medical application for the client and server applications. Section 3 introduces software correctness, including the design by contract and the concept of contract in JML. Section 4 presents the design structure of the application. Section 5 shows the implementation of the HealthCard. Section 6 describes how the HealthCard is verified and validated using JML formal methods tools. Section 7 includes some metrics of the HealthCard implementation and specification. Section 8 presents a short example of how a client-side of a smart card application can be implemented while respecting formal specifications. Section 9 describes a prototype tools to generate JML formal specifications from informal specifications automatically. Section 10 describes some challenges and main ideas came acrorss during the development of the HealthCard. The full formal specification and implementation of the HealthCard smart card application presented in this document can be reached at https://sourceforge.net/projects/healthcard/.

A JML-Based strategy for incorporating formal specifications into the software development process

This thesis presents a JML-based strategy that incorporates formal specifications into the software development process of object-oriented programs. The strategy evolves functional requirements into a “semi-formal” requirements form, and then expressing them as JML formal specifications. The strategy is implemented as a formal-specification pseudo-phase that runs in parallel with the other phase of software development. What makes our strategy different from other software development strategies used in literature is the particular use of JML specifications we make all along the way from requirements to validation-and-verification.

JCML: A specification language for the runtime verification of Java Card programs

COSTA, Umberto Souza; MOREIRA, Anamaria Martins; MUSICANTE, Matin A.; SOUZA NETO, Plácido A. JCML: A specification language for the runtime verification of Java Card programs. Science of Computer Programming. [S.l]: [s.n], 2010.

Specification and Runtime Verification of Java Card Programs

COSTA, Umberto Souza da; MOREIRA, Anamaria Martins; MUSICANTE, Martin A. Specification and Runtime Verification of Java Card Programs. Electronic Notes in Theoretical Computer Science. [S.l:s.n], 2009.

Fertility Rates Following Fixed-Time Artificial Insemination in Dairy Heifers in a Practical Progesterone-Based Protocol

Background: In bovines, more efficient management practices are important for maximizing profitability. In order to increase the pregnancy rates in artificial insemination (AI) programs, several hormonal protocols were developed to synchronize the follicular wave and the moment of ovulation in beef and dairy cattle. In dairy cattle, detection of estrus can be difficult due to a number of factors including the incidence of silent estrus. Hormonal treatments designed to control both luteal and follicular function has permitting efficient synchronizations of time of ovulation. Thus, the AI can be performed in a large number of animals on a fixed schedule without the need for detection of estrus. Using these management techniques, the fixed-time artificial insemination (TAI) can overcome the problem of accurate estrus detection and help in reducing the incidence of repeat breeding. In addition, with TAI in cattle operations, it is possible to facilitate management practices and commercialization, and to reduce the time and semen wasting with animals inseminated at incorrect times. The investigation of practical and efficient TAI protocols is important for reducing the labor and animal handling of TAI in dairy cattle, as well as for increasing the profitability of the cattle management system. This study was carried out in order to investigate the effectiveness of TAI in dairy heifers treated with a practical progesterone-based protocol.Materials, Methods & Results: This experiment was conducted at the university farm located in southwestern Brazil, during May 2009. Thirty-nine cycling crossbred dairy heifers were employed in this study. All animals received a single intramuscular injection of estradiol benzoate and intravaginal progesterone releasing device in a random stage of the estrous cycle (Day 0). on day 7 the animals were treated with PGF2a analogue and on day 9 the device was removed. Forty-eight hours after the device removal (day 11) a synthetic analogue of GnRH was administered and the animals were fixed-time artificially inseminated at the time of GnRH injection. The inseminations were performed using four different batches from the same Holstein bull. Among the heifers that were synchronized (87.2%), 30.8% ovulated until 24 h after TAI and 56.4% ovulated between 24 and 32 h after TAI. The conception rate was 61.5%. No effects of ovulation time in conception rates were detected. The conception rate from heifers that ovulated until 24 h after TAI was 58.3% and from heifers that ovulated between 24 and 32 h after TAI was 77.3%. The mean of ovulatory follicle in heifers that ovulated until 24 h was 14.3 mm and in heifers that ovulated between 24 and 32 h was 11.9 mm.Discussion: Taking together, the findings of the present study, along with those of others, emphasize the concept that development of practical methods for TAI offers significant advantages to dairy producers if conception rates are close or greater to those obtained after breeding at detected estrus. Thus, the results of the present study reinforce the possibility of making dairy cattle production more cost-effective using TAI. In conclusion, with the progesterone-based TAI protocol of the present experiment all synchronized animals ovulated up to 32 h after GnRH+TAI and no effects of ovulation time related to conception rate was detected. The exogenous control of luteal and follicular development facilitated the reproductive management and animal handling. Also, inseminating the heifers at the moment of GnRH injection in a progesterone-based TAI protocol is a practical strategy and provided satisfactory results regarding ovulation and conception rates in dairy heifers.

Spray layer-by-layer films based on phospholipid vesicles aiming sensing application via e-tongue system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)