The Exploitation of Versatile Building Blocks for the Self-Assembly of Novel Molecular Magnets

Using molecular building blocks to self-assemble lattices supporting long-range magnetic order is currently an active area of solid-state chemistry. Consequently, it is the realm of supramolecular chemistry that synthetic chemists are turning to in order to develop techniques for the synthesis of structurally well-defined supramolecular materials. In recent years we have investigated the versatility and usefulness of two classes of molecular building blocks, namely, tris-oxalato transition-metal (M. Pilkington and S. Decurtins, in “Magnetoscience—From Molecules to Materials,” Wiley–VCH, 2000), and octacyanometalate complexes (Pilkington and Decurtins, Chimia 54, 593 (2001)), for applications in the field of molecule-based magnets. Anionic, tris-chelated oxalato building blocks are able to build up two-dimensional honeycomb-layered structural motifs as well as three-dimensional decagon frameworks. The discrimination between the crystallization of the two- or three-dimensional structures relies on the choice of the templating counterions (Decurtins, Chimia 52, 539 (1998); Decurtins et al. Mol. Cryst. Liq. Cryst. 273, 167 (1995); New J. Chem. 117 (1998)). These structural types display a range of ferro, ferri, and antiferromagnetic properties (Pilkington and Decurtins, in “Magnetoscience—From Molecules to Materials”). Octacyanometalate building blocks self-assemble to afford two new classes of cyano-bridged compounds namely, molecular clusters and extended three dimensional networks (J. Larionova et al., Angew. Chem. Int. Ed. 39, 1605 (2000); Pilkington et al., in preparation). The molecular cluster with a MnII9MoV6 core has the highest ground state spin value, S=51/2, reported to-date (Larionova et al., Angew. Chem. Int. Ed. 39, 1605 (2000)). In the high-temperature regime, the magnetic properties are characterized by ferromagnetic intracluster coupling. In the magnetic range below 44 K, the magnetic cluster signature is lost as possibly a bulk behavior starts to emerge. The three-dimensional networks exhibit both paramagnetic and ferromagnetic behavior, since the magnetic properties of these materials directly reflect the electronic configuration of the metal ion incorporated into the octacyanometalate building blocks (Pilkington et al., in preparation). For both the oxalate- and cyanide-bridged materials, we are able to manipulate the magnetic properties of the supramolecular assemblies by tuning the electronic configurations of the metal ions incorporated into the appropriate molecular building blocks (Pilkington and Decurtins, in “Magnetoscience—From Molecules to Materials,” Chimia 54, 593 (2000)).

A comparison of labor and delivery management activities in two settings

Similarities and differences in management activities and patient health outcomes between a traditional physician staffed labor and delivery setting and a certified nurse-midwife staffed Birth Center within the same hospital were described. The 950 study subjects, low income, minority women, were classified as low obstetrical risk by a POPRAS score of 25 points or less at time of admission for labor and delivery. The study subjects were similar in demographic, antepartum and intrapartum characteristics; the labor course was problem free for the majority in both settings. There were no remarkable differences in health outcomes between the groups. Management activities varied between settings; these variations were policy related rather than health related. The POPRAS rating system was an accurate predictor for 93% of BC subjects and 85% of LDU subjects. Charge for service was approximately $600 less for BC women; length of stay did not contribute to the difference in charge. Overall, BC respondents to the attitude survey were more satisfied with their labor and delivery experience than L\&DU women. ^

Decent employment and subjectivity in the workplace : Notes for an agenda of labor policies in citizenship terms

Retomando los problemas contemporáneos del trabajo en términos de sus actores, se examinan los aspectos en los cuales la psicología de trabajo puede producir contribuciones y reflexiones. El problema del diagnóstico así como el de la comprensión y la elucidación de los límites y alcance que las políticas de empleo implican diseños diferentes para procesos ligados a los aspectos psicosociales del trabajo, que exceden a los determinados desde el punto de vista del empleo decente.

Decent employment and subjectivity in the workplace : Notes for an agenda of labor policies in citizenship terms

Retomando los problemas contemporáneos del trabajo en términos de sus actores, se examinan los aspectos en los cuales la psicología de trabajo puede producir contribuciones y reflexiones. El problema del diagnóstico así como el de la comprensión y la elucidación de los límites y alcance que las políticas de empleo implican diseños diferentes para procesos ligados a los aspectos psicosociales del trabajo, que exceden a los determinados desde el punto de vista del empleo decente.

Decent employment and subjectivity in the workplace : Notes for an agenda of labor policies in citizenship terms

Retomando los problemas contemporáneos del trabajo en términos de sus actores, se examinan los aspectos en los cuales la psicología de trabajo puede producir contribuciones y reflexiones. El problema del diagnóstico así como el de la comprensión y la elucidación de los límites y alcance que las políticas de empleo implican diseños diferentes para procesos ligados a los aspectos psicosociales del trabajo, que exceden a los determinados desde el punto de vista del empleo decente.

The Changing Nature of Employment and the Reform of Labor and Social Security Legislation in Post-Apartheid South Africa

This paper tries to understand the current status of South African labor market, which is changing in contradictory directions, i.e. a strengthening of the rights and protection of workers at the same time as the flexibilization of employment, in the context of the characteristics of labor and social security legislation in South Africa, as well as the nature of labor and social security reforms after democratization. We put emphasis on the corporatist nature of labor policy-making as the factor influencing the course of reforms; it is argued that the apparently contradictive changes can be explained consistently by the corporatist labor policy-making process which has been practiced notwithstanding the problem of representativeness.

Backward-bending of labor supply function and free riders

It seems like that backward- bending of labor supply function can be observed in Central Asian Countries such as Uzbekistan and Kazakhstan. People’s basic needs of life are satisfied and they do not increase labor supplies even if wage increases. It is possible to find some cases in which slowdowns increase, when a manager in a firm enforces penalties for workers have slowdowns. This phenomenon occurs because a worker prefers the position of equilibrium on the labor supply function always in the upper direction. This article explains the increase of free-riders by penalties and how to avoid them.

Authoritarianism and labor market : preference of labor policies in the Arab Gulf countries

Migrant and labor issues are a primary concern in the Arab Gulf countries. With focus on the economic and political conditions that influence actors' decisions when framing labor policies, this study analyzes how preferences of such policies are formed and explains why the governments of the Arab Gulf countries attempt to implement less economical policies. The findings suggest that governments avoid concessions for enterprises required to implement more economical policies and chose uneconomical ones to maintain authoritarian regimes.

Automatic exploitation of non-determinate independent and-parallelism in the basic andorra model

Andorra-I is the first implementation of a language based on the Andorra Principie, which states that determinate goals can (and shonld) be run before other goals, and even in a parallel fashion. This principie has materialized in a framework called the Basic Andorra model, which allows or-parallelism as well as (dependent) and-parallelism for determinate goals. In this report we show that it is possible to further extend this model in order to allow general independent and-parallelism for nondeterminate goals, withont greatly modifying the underlying implementation machinery. A simple an easy way to realize such an extensión is to make each (nondeterminate) independent goal determinate, by using a special "bagof" constract. We also show that this can be achieved antomatically by compile-time translation from original Prolog programs. A transformation that fulfüls this objective and which can be easily antomated is presented in this report.

Variable threshold algorithm for division of labor analyzed as a dynamical system

Division of labor is a widely studied aspect of colony behavior of social insects. Division of labor models indicate how individuals distribute themselves in order to perform different tasks simultaneously. However, models that study division of labor from a dynamical system point of view cannot be found in the literature. In this paper, we define a division of labor model as a discrete-time dynamical system, in order to study the equilibrium points and their properties related to convergence and stability. By making use of this analytical model, an adaptive algorithm based on division of labor can be designed to satisfy dynamic criteria. In this way, we have designed and tested an algorithm that varies the response thresholds in order to modify the dynamic behavior of the system. This behavior modification allows the system to adapt to specific environmental and collective situations, making the algorithm a good candidate for distributed control applications. The variable threshold algorithm is based on specialization mechanisms. It is able to achieve an asymptotically stable behavior of the system in different environments and independently of the number of individuals. The algorithm has been successfully tested under several initial conditions and number of individuals.

Methods and Techniques for the Generation and Eficient Exploitation of RDB2RDF Mappings

RDB to RDF Mapping Language (R2RML) es una recomendación del W3C que permite especificar reglas para transformar bases de datos relacionales a RDF. Estos datos en RDF se pueden materializar y almacenar en un sistema gestor de tripletas RDF (normalmente conocidos con el nombre triple store), en el cual se pueden evaluar consultas SPARQL. Sin embargo, hay casos en los cuales la materialización no es adecuada o posible, por ejemplo, cuando la base de datos se actualiza frecuentemente. En estos casos, lo mejor es considerar los datos en RDF como datos virtuales, de tal manera que las consultas SPARQL anteriormente mencionadas se traduzcan a consultas SQL que se pueden evaluar sobre los sistemas gestores de bases de datos relacionales (SGBD) originales. Para esta traducción se tienen en cuenta los mapeos R2RML. La primera parte de esta tesis se centra en la traducción de consultas. Se propone una formalización de la traducción de SPARQL a SQL utilizando mapeos R2RML. Además se proponen varias técnicas de optimización para generar consultas SQL que son más eficientes cuando son evaluadas en sistemas gestores de bases de datos relacionales. Este enfoque se evalúa mediante un benchmark sintético y varios casos reales. Otra recomendación relacionada con R2RML es la conocida como Direct Mapping (DM), que establece reglas fijas para la transformación de datos relacionales a RDF. A pesar de que ambas recomendaciones se publicaron al mismo tiempo, en septiembre de 2012, todavía no se ha realizado un estudio formal sobre la relación entre ellas. Por tanto, la segunda parte de esta tesis se centra en el estudio de la relación entre R2RML y DM. Se divide este estudio en dos partes: de R2RML a DM, y de DM a R2RML. En el primer caso, se estudia un fragmento de R2RML que tiene la misma expresividad que DM. En el segundo caso, se representan las reglas de DM como mapeos R2RML, y también se añade la semántica implícita (relaciones de subclase, 1-N y M-N) que se puede encontrar codificada en la base de datos. Esta tesis muestra que es posible usar R2RML en casos reales, sin necesidad de realizar materializaciones de los datos, puesto que las consultas SQL generadas son suficientemente eficientes cuando son evaluadas en el sistema gestor de base de datos relacional. Asimismo, esta tesis profundiza en el entendimiento de la relación existente entre las dos recomendaciones del W3C, algo que no había sido estudiado con anterioridad. ABSTRACT. RDB to RDF Mapping Language (R2RML) is a W3C recommendation that allows specifying rules for transforming relational databases into RDF. This RDF data can be materialized and stored in a triple store, so that SPARQL queries can be evaluated by the triple store. However, there are several cases where materialization is not adequate or possible, for example, if the underlying relational database is updated frequently. In those cases, RDF data is better kept virtual, and hence SPARQL queries over it have to be translated into SQL queries to the underlying relational database system considering that the translation process has to take into account the specified R2RML mappings. The first part of this thesis focuses on query translation. We discuss the formalization of the translation from SPARQL to SQL queries that takes into account R2RML mappings. Furthermore, we propose several optimization techniques so that the translation procedure generates SQL queries that can be evaluated more efficiently over the underlying databases. We evaluate our approach using a synthetic benchmark and several real cases, and show positive results that we obtained. Direct Mapping (DM) is another W3C recommendation for the generation of RDF data from relational databases. While R2RML allows users to specify their own transformation rules, DM establishes fixed transformation rules. Although both recommendations were published at the same time, September 2012, there has not been any study regarding the relationship between them. The second part of this thesis focuses on the study of the relationship between R2RML and DM. We divide this study into two directions: from R2RML to DM, and from DM to R2RML. From R2RML to DM, we study a fragment of R2RML having the same expressive power than DM. From DM to R2RML, we represent DM transformation rules as R2RML mappings, and also add the implicit semantics encoded in databases, such as subclass, 1-N and N-N relationships. This thesis shows that by formalizing and optimizing R2RML-based SPARQL to SQL query translation, it is possible to use R2RML engines in real cases as the resulting SQL is efficient enough to be evaluated by the underlying relational databases. In addition to that, this thesis facilitates the understanding of bidirectional relationship between the two W3C recommendations, something that had not been studied before.

Mechanism-based inhibition of the melatonin rhythm enzyme: Pharmacologic exploitation of active site functional plasticity

Serotonin N-acetyltransferase is the enzyme responsible for the diurnal rhythm of melatonin production in the pineal gland of animals and humans. Inhibitors of this enzyme active in cell culture have not been reported previously. The compound N-bromoacetyltryptamine was shown to be a potent inhibitor of this enzyme in vitro and in a pineal cell culture assay (IC50 ≈ 500 nM). The mechanism of inhibition is suggested to involve a serotonin N-acetyltransferase-catalyzed alkylation reaction between N-bromoacetyltryptamine and reduced CoA, resulting in the production of a tight-binding bisubstrate analog inhibitor. This alkyltransferase activity is apparently catalyzed at a functionally distinct site compared with the acetyltransferase activity active site on serotonin N-acetyltransferase. Such active site plasticity is suggested to result from a subtle conformational alteration in the protein. This plasticity allows for an unusual form of mechanism-based inhibition with multiple turnovers, resulting in “molecular fratricide.” N-bromoacetyltryptamine should serve as a useful tool for dissecting the role of melatonin in circadian rhythm as well as a potential lead compound for therapeutic use in mood and sleep disorders.

Division of Labor among the α6β4 Integrin, β1 Integrins, and an E3 Laminin Receptor to Signal Morphogenesis and β-Casein Expression in Mammary Epithelial Cells

Contact of cultured mammary epithelial cells with the basement membrane protein laminin induces multiple responses, including cell shape changes, growth arrest, and, in the presence of prolactin, transcription of the milk protein β-casein. We sought to identify the specific laminin receptor(s) mediating the multiple cell responses to laminin. Using assays with clonal mammary epithelial cells, we reveal distinct functions for the α6β4 integrin, β1 integrins, and an E3 laminin receptor. Signals from laminin for β-casein expression were inhibited in the presence of function-blocking antibodies against both the α6 and β1 integrin subunits and by the laminin E3 fragment. The α6-blocking antibody perturbed signals mediated by the α6β4 integrin, and the β1-blocking antibody perturbed signals mediated by another integrin, the α subunit(s) of which remains to be determined. Neither α6- nor β1-blocking antibodies perturbed the cell shape changes resulting from cell exposure to laminin. However, the E3 laminin fragment and heparin both inhibited cell shape changes induced by laminin, thereby implicating an E3 laminin receptor in this function. These results elucidate the multiplicity of cell-extracellular matrix interactions required to integrate cell structure and signaling and ultimately permit normal cell function.

Expression of a Hox gene, Cnox-2, and the division of labor in a colonial hydroid

We report the isolation and expression of the Hox gene, Cnox-2, in Hydractinia symbiolongicarpus, a hydrozoan displaying division of labor. We found different patterns of aboral-to-oral Cnox-2 expression among polyp polymorphs, and we show that experimental conversion of one polyp type to another is accompanied by concordant alteration in Cnox-2 expression. Our results are consistent with the suggestion that polyp polymorphism, characteristic of hydractiniid hydroids, arose via evolutionary modification of proportioning of head to body column.