Orthogonal protecting groups in the synthesis of tryptophanyl-hexahydropyrroloindoles

The synthesis of various polycyclic systems containing a C3a-Ni bond between a hexahydropyrrolo[2,3-b]indole and an indole tryptophan is described here. A series of experiments were performed to determine the best combination of five orthogonal protecting groups and the best reaction conditions for formation of said bond, which is a common feature among many recently discovered marine natural products.

Topological phases in small quantum Hall samples

Topological order has proven a useful concept to describe quantum phase transitions which are not captured by the Ginzburg-Landau type of symmetry-breaking order. However, lacking a local order parameter, topological order is hard to detect. One way to detect it is via direct observation of anyonic properties of excitations which are usually discussed in the thermodynamic limit, but so far has not been realized in macroscopic quantum Hall samples. Here we consider a system of few interacting bosons subjected to the lowest Landau level by a gauge potential, and theoretically investigate vortex excitations in order to identify topological properties of different ground states. Our investigation demonstrates that even in surprisingly small systems anyonic properties are able to characterize the topological order. In addition, focusing on a system in the Laughlin state, we study the robustness of its anyonic behavior in the presence of tunable finite-range interactions acting as a perturbation. A clear signal of a transition to a different state is reflected by the system's anyonic properties.

The efficiency of indicator groups for the conservation of amphibians in the Brazilian Atlantic Forest

The adequate selection of indicator groups of biodiversity is an important aspect of the systematic conservation planning. However, these assessments differ in the spatial scale, in the methods used and in the groups considered to accomplish this task, which generally produces contradictory results. The quantification of the spatial congruence between species richness and complementarity among different taxonomic groups is a fundamental step to identify potential indicator groups. Using a constructive approach, the main purposes of this study were to evaluate the performance and efficiency of eight potential indicator groups representing amphibian diversity in the Brazilian Atlantic Forest. Data on the geographic range of amphibian species that occur in the Brazilian Atlantic Forest was overlapped to the full geographic extent of the biome, which was divided into a regular equal-area grid. Optimization routines based on the concept of complementarily were applied to verify the performance of each indicator group selected in relation to the representativeness of the amphibians in the Brazilian Atlantic Forest as a whole, which were solved by the algorithm"simulated annealing", through the use of the software MARXAN. Some indicator groups were substantially more effective than others in regards to the representation of the taxonomic groups assessed, which was confirmed by the high significance of data (F = 312.76; p < 0.01). Leiuperidae was considered as the best indicator group among the families analyzed, as it showed a good performance, representing 71% of amphibian species in the Brazilian Atlantic Forest (i.e. 290 species), which may be associated with the diffuse geographic distribution of its species. This study promotes understanding of how the diversity standards of amphibians can be informative for systematic conservation planning on a regional scale.

Normal values for pancreatic stone protein in different age groups.

BACKGROUND: Pancreatic stone protein (PSP) has been identified as a promising sepsis marker in adults, children and neonates. However, data on population-based reference values are lacking. This study aimed to establish age-specific reference values for PSP. METHODS: PSP was determined using a specific ELISA. PSP serum concentrations were determined in 372 healthy subjects including 217 neonates, 94 infants and children up to 16 years, and 61 adults. The adjacent categories method was used to determine which age categories had significantly different PSP concentrations. RESULTS: PSP circulating levels were not gender-dependent and ranged from 1.0 to 99.4 ng/ml with a median of 9.2 ng/ml. PSP increased significantly between the age categories, from a median of 2.6 ng/ml in very preterm newborns, to 6.3 ng/ml in term newborns, to 16.1 ng/ml in older children (p < 0.001). PSP levels were higher on postnatal day three compared to levels measured immediately post delivery (p < 0.001). Paired umbilical artery and umbilical vein samples were strongly correlated (p < 0.001). Simultaneously obtained capillary heel-prick versus venous samples showed a good level of agreement for PSP (Rho 0.89, bias 19 %). CONCLUSIONS: This study provides age-specific normal values that may be used to define cut-offs for future trials on PSP. We demonstrate an age-dependent increase of PSP from birth to childhood.

World Polarization in carbon emissions, potential conflict and groups: an updated revision

Typically, conflicts in world environmental negotiations are related, amongst other aspects, to the level of polarization of the countries in groups with conflicting interests. Given the predictable relationship between polarization and conflict, it would seem logical to evaluate the degree to which the distribution of countries – for example, in terms of their CO2 emissions per capita – would be structured through groups which in themselves are antagonistic, as well as their evolution over time. This paper takes the concept of polarization to explore this distribution for the period 1992-2010, looking at different analytic approaches related to the concept. Specifically, it makes a comparative evaluation of the results associated with endogenous multi-polarization measures (i.e. EGR and DER indices), exogenous measures (i.e. Z-K or multidimensional index) and strict bipolarization measures (i.e. Wolfson’s measure). Indeed, the interest lies not only in evaluating the global situation of polarization by comparing the different approaches and their temporal patterns, but also in examining the explanatory capacity of the different proxy groups used as a possible reference for designing global environmental policy from a group premise. JEL codes: D39; Q43; Q56. Key words: polarization; carbon emissions; conflict;

Versatile methodology to hydrate alkynes, in the presence of a wide variety of functional groups, with Mercury(II) p-Toluensulfonamidate, under catalytic, mild and neutral conditions

A method to generate carbonylic compounds from alkynes under mild and neutral conditions, with excellent functional group compatibility and high yields, is described. Hydration takes place under catalytic conditions by using from 0.1 to 0.2 equivalents of the easily available and inexpensive mercury(II) p-toluensulfonamidate in a hydroalcoholic solution. After use the catalyst is iner tized and/or recycled ...

Computing the diameter of Coxeter groups

This thesis addresses the problem of computing the minimal and maximal diameter of the Cayley graph of Coxeter groups. We first present and assert relevant parts of polytope theory and related Coxeter theory. After this, a method of contracting the orthogonal projections of a polytope from Rd onto R2 and R3, d ¸ 3 is presented. This method is the Equality Set Projection algorithm that requires a constant number of linearprogramming problems per facet of the projection in the absence of degeneracy. The ESP algorithm allows us to compute also projected geometric diameters of high-dimensional polytopes. A representation set of projected polytopes is presented to illustrate the methods adopted in this thesis.

Convergent Approaches for the Synthesis of the Anti-tumoral Peptide, Kahalalide F. Study of Orthogonal Protecting Groups

Kahalalide compounds are peptides that are isolated from a Hawaiian herbivorous marine species of mollusc, Elysia rufescens, and its diet, the green alga Bryopsis sp. Kahalalide F and its synthetic analogues are the most promising compounds of the Kahalalide family because they show anti-tumoral activity. Linear solid-phase syntheses of Kahalalide F have been reported. Here we describe several new improved synthetic routes based on convergent approaches with distinct orthogonal protection schemes for the preparation of Kahaladide analogues. These strategies allow a better control and characterization of the intermediates because more reactions are performed in solution. Five derivatives of Kahalalide F were synthesized using several convergent approaches.

On Topological Solitons in The Faddeev-Skyrme Model and its Extensions

The topological solitons of two classical field theories, the Faddeev-Skyrme model and the Ginzburg-Landau model are studied numerically and analytically in this work. The aim is to gain information on the existence and properties of these topological solitons, their structure and behaviour under relaxation. First, the conditions and mechanisms leading to the possibility of topological solitons are explored from the field theoretical point of view. This leads one to consider continuous deformations of the solutions of the equations of motion. The results of algebraic topology necessary for the systematic treatment of such deformations are reviewed and methods of determining the homotopy classes of topological solitons are presented. The Faddeev-Skyrme and Ginzburg-Landau models are presented, some earlier results reviewed and the numerical methods used in this work are described. The topological solitons of the Faddeev-Skyrme model, Hopfions, are found to follow the same mechanisms of relaxation in three different domains with three different topological classifications. For two of the domains, the necessary but unusual topological classification is presented. Finite size topological solitons are not found in the Ginzburg-Landau model and a scaling argument is used to suggest that there are indeed none unless a certain modification to the model, due to R. S. Ward, is made. In that case, the Hopfions of the Faddeev-Skyrme model are seen to be present for some parameter values. A boundary in the parameter space separating the region where the Hopfions exist and the area where they do not exist is found and the behaviour of the Hopfion energy on this boundary is studied.

Strategic groups and performance: an empirical analysis of strategic groups in the wind energy industry in Europe

The strategic group theory provides an intermediate level of analysis between a single company and the whole industry for identifying issues about the company's competitive position and strategic choices. Strategic groups are companies within an industry with similar strategic characteristics or competing on similar bases. Strategic choices are aligned with the firms’ resources. The purpose of this study was to identify the strategic groups in the wind energy industry in Europe, and study, whether a certain group membership results in financial performance differences. Altogether 80 European wind energy companies were included in the study, which were clustered into four strategic groups according to their age and growth rate. Each group corresponds to a different strategy. The results show that the wind energy companies can be clustered according to the chosen strategic characteristics. Strategic decisions were investigated with characteristic variables. Performance variables were used in the analysis measuring profitability, liquidity and solvency of the groups. These strategic choices of the companies did not have a significant influence on the firms’ performance. The more mature and slower growing group proved to be the most successful. However, the differences between groups were generally not statistically significant. The only statistically significant difference found was in the solvency ratio between Mature Slow and Young Rapid groups. Measured with these variables, more mature and slower growing companies performed better. Therefore, a certain strategic group membership results in performance differences.

A Note on the periodic orbits and topological entropy of graph maps

This paper deals with the relationship between the periodic orbits of continuous maps on graphs and the topological entropy of the map. We show that the topological entropy of a graph map can be approximated by the entropy of its periodic orbits

Essential factors for control of the equilibrium in the reversible rearrangement of M3N@Ih-C80 fulleropyrrolidines: Exohedral functional groups versus endohedral metal clusters

The effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@Ih-C80 products from the Prato reaction through [1,5]-sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]-isomer (kinetic product) and the [5,6]-isomer. In all the derivatives, the [6,6]- and [5,6]-Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal-cluster size. Further DFT calculations and 13C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]- and [5,6]-fulleropyrrolidines