Synthesis, molecular structure and physicochemical properties of bis(3 `-azido-3 `-deoxythymidin-5 `-yl) carbonate

3`-Azido-3`-deoxythymidine (zidovudine, AZT), a synthetic analog of natural nucleoside thymidine, has been used extensively in AIDS treatments. We report here the synthesis. X-ray crystal and molecular structure, NMR, IR and Raman spectra and the thermal behavior of a novel carbonate of AZT [(AZT-O)(2)C=O], prepared by the reaction of zidovudine with carbonyldiimidazole. The carbonate compound, C(21)H(24)N(10)O(9), crystallizes in the tetragonal space group P4(1)2(1)2 with a = b = 15.284(1), c = 21.695(1) angstrom, and Z = 8 molecules per unit cell. It consists of two AZT moieties of closely related conformations which are bridged by a carbonyl group to adopt a folded Z-like shape. (C) 2010 Elsevier B.V. All rights reserved.

Structure and thermal reactivity of Zn(II) salts of isocinchomeronic acid (2,5-pyridinedicarboxylic acid)

The synthesis, an improved refined crystal and molecular structure re-determination, and the thermal decomposition behavior of two Zn(II) derivatives of isocinchomeronic acid (2,5-pyridinedicarboxylic acid or H(2)2,5-pydc) are presented. [Zn(2,5-pydc)(H(2)O)(3)Zn(2,5-pydc)(H(2)O)(2)](2) (1) crystallizes in the triclinic P-1 space group with a = 7.106(2), b = 11.450(2), c = 11.869(1) angstrom, alpha = 107.29(1), beta = 104.08(1), gamma = 90.32(2)degrees, and Z = 2. [Zn(2,5-pydc)(H(2)O)(2)] center dot H(2)O (2) is orthorhombic (P2(1)2(1)2(1) space group), with a = 7.342(1), b = 9.430(1), c = 13.834(2) angstrom, and Z = 4. The structures were refined to agreement R(1)-factors of 0.0315 (1) and 0.0336 (2). Complex (1) is arranged as molecular Zn(4)(2,5-pydc)(4)(H(2)O)(10) tetramers, the cages of which define channels that remain unblocked by anions. Compound (2) is polymeric with Zn(2,5-pydc)(H(2)O)(2) and Zn(2,5-pydc)(H(2)O)(3) units linked through bridging ligands. Both compounds were synthesized under mild conditions in aqueous media, without need to resort to hydrothermal media. Changing the pH from 4.51 to 5.75 suffices to direct the chemical processes toward the orthorhombic compound rather than to the triclinic one.

Structure-activity relationships of hypervalent organochalcogenanes as inhibitors of cysteine cathepsins V and S

A new series of organotelluranes were synthesized and investigated, and the structure-activity relationships in cysteine proteases inhibition were determinated. It was possible to identify the relevance of structural components linked to the reactivity of these compounds as inhibitors. For example, dibromo-organotelluranes showed to be more reactive than dichloro-organotelluranes towards cysteine cathepsins V and S. Besides, no remarkable enantio-selectivity was verified. In general the achiral organotelluranes were more reactive than the chiral congeners against cysteine cathepsins V and S. A reactivity order for organochalcogenanes and cysteine cathepsins was proposed after the comparison of the inhibitory potencies of organotelluranes with the related organoselenanes. (C) 2011 Elsevier Ltd. All rights reserved.

Analysis of Structure and Tendencies of Qualified Immigrant Workforce on the Swedish Labor Market

The purpose of this paper is to make quantitative and qualitative analysis of foreign citizens who may participate on the Swedish labor market (in text refers to as ‘immigrants’). This research covers the period 1973-2005 and gives prediction figures of immigrant population, age and gender structure, and education attainment in 2010. To cope with data regarding immigrants from different countries, the population was divided into six groups. The main chapter is divided into two parts. The first part specifies division of immigrants into groups by country of origin according to geographical, ethnical, economical and historical criteria. Brief characteristics and geographic position, dynamic and structure description were given for each group; historical review explain rapid changes in immigrant population. Statistical models for description and estimation future population were given. The second part specifies education and qualification level of the immigrants according to international and Swedish standards. Models for estimating age and gender structure, level of education and professional orientation of immigrants in different groups are given. Inferences were made regarding ethnic, gender and education structure of immigrants; the distribution of immigrants among Swedish counties is given. Discussion part presents the results of the research, gives perspectives for the future brief evaluation of the role of immigrants on the Swedish labor market.

Assessing Dodd Frank Effects on banking capital structure and Banker´s Pay structure

The systemic financial crisis that started in 2008 in the United States had some severe effects in the economic activity and required the bailout of financial institutions with the use of taxpayer’s money. It also originated claims for stronger regulatory framework in order to avoid another threat in the financial market. The Dodd Frank Act was proposed and approved in the United States in the aftermath of the crisis and brought, among many other features, the creation of the Financial Stability Oversight Council and the tougher inspection of financial institutions with asset above 50 billion dollars. The objective of this work is to study the causal effect of the Dodd Frank Act on the behavior of the treatment group subject to monitoring by the Financial Stability Oversight Council (financial institutions with assets above 50 billion dollars) regarding capital and compensation structure in comparison to the group that was not treated. We use data from Compustat and our empirical strategy is the Regression Discontinuity Design, not usually applied to the banking literature, but very useful for the present work since it allows us to compare the treatment group and the non-treatment group in the year of the enactment of the law (2010). No change of behavior was observed for the Capital Structure. In the Compensation Schemes, however, a decrease was found in the item other compensation for CEOs and CFOs. We also performed a robustness check by running a placebo test on the variables in the year before the law was enacted. No significance was found, which supports the conclusion that our main results were caused by the enactment of the DFA.

Independent and interactive effects of a top and an intermediate fish species on the food web structure of a tropical stream

Two fish species, one top predator (Imparfinis mirini) and one intermediate detritivorous species (Hisonotus depressicauda), were experimentally manipulated to evaluate their relative importance in structuring the periphytic community, as well as their effects on the other trophic levels. An enclosure experiment was conducted in the Potreirinho creek, a second order tributary of Paranapanema River, SE Brazil. Five treatments were used: enclosure of the predator species. enclosure of the detritivorous species, enclosure of both together, exclusion of all fish species (closed control cage), and cage open to all fish community, (open control). Through direct and indirect effects, I. mirini, when alone gave rise to a trophic cascade that resulted in a positive effect on algal resources. Through direct effects, H. depressicauda. when alone, reduced the amount of organic matter, resulting in a positive indirect effect on algae. In addition, when the two species were enclosed together, only the effects determined by the detritivorous species were present. The results indicate the important role of the intermediate detritivorous species in the maintenance of the composition and trophic structure of the analyzed community by reducing the effects caused by the top predator.

Embryology and seed development of Blastocaulon scirpeum and Paepalanthus scleranthus (Eriocaulaceae)

The embryology and seed structure of Blastocaulon scirpeum (Mart.) Giul. and Paepalanthus scleranthus Ruhland were studied in order to contribute to the embryology of Eriocaulaceae and supply data for future taxonomic studies. Both species present: anther with 4-layered wall; conspicuous endothecium with fibrous thickenings; secretory tapetum with uninucleate cells; successive microsporogenesis forming isobilateral microspore tetrads; bicellular pollen grains; orthotropous, bitegmic and tenuinucellate ovule; micropyle formed by the inner integument alone; megagametophyte of the Polygonum type, with a conspicuous antipodal cyst; nuclear and starchy endosperm; reduced, undifferentiated, and bell-shaped embryo; operculate and endotestal seed; seed coat derived from the two ovule integuments; and tanniniferous endotegmen. In addition, Blastocaulon scirpeum shows a bisporangiate anther and a 3-layered ovary wall, while P. scleranthus presents a tetrasporangiate anther that becomes bisporangiate at maturity, and a 2-layered ovary wall. This investigation shows that the bisporangiate condition does not suffice to separate Blastocaulon from Paepalanthus, since it is common to both. It also indicates, based on several embryological aspects, the proximity of Eriocaulaceae and Xyridaceae, which comply mainly with the features presented by the other commelinid families. These results may be used in future cladistic analysis of the family, and contribute to a better understanding of its phylogeny.

New insights regarding HCV-NS5A structure/function and indication of genotypic differences

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

Voltage-composition profile and synchrotron X-ray structural analysis of low and high temperature LixCoO2 host material

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

Automated NMR structure determination and disulfide bond identification of the myotoxin crotamine from Crotalus durissus terrificus

Crotamine is one of four major components of the venom of the South American rattlesnake Crotalus durissus terrificus. Similar to its counterparts in the family of the myotoxins, it induces myonecrosis of skeletal muscle cells. This paper describes a new NMR structure determination of crotamine in aqueous solution at pH 5.8 and 20 degrees C, using standard homonuclear (1)H NMR spectroscopy at 900 MHz and the automated structure calculation software ATNOS/CANDID/DYANA. The automatic NOESY spectral analysis included the identification of a most likely combination of the six cysteines into three disulfide bonds, i.e. Cys4-Cys36, Cys11-Cys30 and Cys18-Cys37; thereby a generally applicable new computational protocol is introduced to determine unknown disulfide bond connectivities in globular proteins. A previous NMR structure determination was thus confirmed and the structure refined. Crotamine contains an alpha-helix with residues 1-7 and a two-stranded anti-parallel beta-sheet with residues 9-13 and 34-38 as the only regular secondary structures. These are connected with each other and the remainder of the polypeptide chain by the three disulfide bonds, which also form part of a central hydrophobic core. A single conformation was observed, with Pro13 and Pro21 in the trans and Pro20 in the cis-form. The global fold and the cysteine-pairing pattern of crotamine are similar to the beta-defensin fold, although the two proteins have low sequence homology, and display different biological activities. (c) 2005 Elsevier Ltd. All rights reserved.

Flowering phenology, nectary structure and breeding system in Corymborkis flava (Spiranthoideae : Tropidieae), a terrestrial orchid from a Neotropical forest

Flowering phenology, breeding system and nectary structure of Corymborkis flava (Sw.) Kuntze were studied in a fragment of the Atlantic Forest in south-eastern Brazil. The flowering period extended from March (end of rainy season) to early June and seed dispersal occurred from June to September (dry season). Flowering peak occurred mainly in April, with up to 34 open flowers per plant being observed. The yellow, odourless and tubular flowers lasted similar to 7.8 days. The flowers present a perigonal nectary located in the basal lateral parts of the labellum; this is the first report on the nectary location and characterisation in the Tropidieae tribe. At the pre-anthesis stage, cells of both secretory parenchyma and epidermis of the nectary are filled with compound amyloplasts. However, starch grains were not observed in these tissues in senescent flowers, indicating that these starch grains are hydrolysed and used as source of sugars for nectar production. The nectar accumulates between the cuticle and the outer periclinal wall of the epidermal cells before. owing out into the nectar chamber. C. flava is a self-compatible species and spontaneous self-pollination does not occur because of hercogamy. The high pollinia removal (0.80) and insertion (0.82) per flower, as well as the high natural fruit-set indicate an efficient natural pollination system. The present study contributes for the knowledge of the diversity of reproductive strategies and nectary structures in Orchidaceae.

Development of successive cambia and structure of wood in Gallesia integrifolia (Spreng.) Harms (Phytolaccaceae)

Stem diameter in Gallesia integrifolia (Spreng.) Harms (Phytolaccaceae) increases by forming concentric rings of xylem alternating with phloem, which show frequent anastomoses. After a period of primary growth and the formation of first (normal) ring of vascular cambium, further successive rings are initiated outside this cambium. The second ring of cambium originates from the pericycle parenchyma located between the proto-phloem, and the pericycle fibres. Each cambium produces centripetally secondary xylem and centrifugally secondary phloem. Differentiation of xylem precedes that of phloem and the first elements formed are always xylem fibres. Structurally, the vascular cylinder is composed by successive rings of secondary xylem and phloem. These rings are separated by wide bands of conjunctive parenchyma tissue. Presence of collateral vascular bundles with irregular orientation is observed in the region of anastomoses of two or more bands of conjunctive tissue. These bundles are surrounded by isodiametric, lignified and thick-walled cells. In some of the cambial rings, occurrence of polycentric rays was also noticed; these rays are tall, and characterized by the presence of meristematic regions that differentiated into thick-walled elements of secondary xylem. Origin and development of the successive cambia and the structure of xylem are discussed.

Structure and Properties of Barium Bismuth Titanate Prepared by Mechanochemical Synthesis

Bi4Ti4O15 [BBT], a member of Aurivillius bismuth-based layer-structure perovskites, was prepared from stoichiometric amounts of BaTiO3 [BT] and Bi4Ti3O12 [BIT] obtained via mechanochemical synthesis. Mechanochemical synthesis was performed in air atmosphere in a planetary ball mill. BBT ceramics were sintered at 1100C for 4 h without pre-calcination step within heating rate 10C/min. The formation of phase and crystal structure of BT, BIT and BBT were approved using X-ray analysis. The morphology of obtained powders and microstructure were exhamined using scanning electron microscopy. The electrical properties of sintered samples were carried out.

Influence of silver additions on the structure and phase transformation of the Cu-13 wt % Al alloy

The influence of silver additions on the structure and phase transformation of the Cu-13 wt % Al alloy was studied by differential thermal analysis, X-ray diffraction, scanning electron microscopy and energy dispersive analysis of X-rays. The results indicate that the presence of silver modifies the phase-stability field, the transition temperature and the structure of the alloy. These effects are more pronounced for silver concentrations up to 8 wt %.

Initial description of the phylogeography, population structure and genetic diversity of Atlantic spotted dolphins from Brazil and the Caribbean, inferred from analyses of mitochondrial and nuclear DNA

We provide initial information regarding the population structure and genetic diversity of Stenella frontalis from the Caribbean and southeastern Brazil from analyses of mitochondrial control region sequences and sequences from the first intron of the α-lactalbumin gene. Comparisons with previously described S. frontalis sequences showed a high number of haplotypes shared between populations throughout their distribution range. High diversity was found for southeastern Brazil and Caribbean samples, and population structure analyses indicate significant differentiation among population units at the FST level, but not at the ΦST level. Significant differentiation at the FST level was found between the Caribbean population unit and all other populations units. These results suggest historical or present connectivity between the Azores and Madeira and the southeastern Brazil groups and population differentiation between the Caribbean and southeastern Brazil, supporting the notion of two separate stocks in the waters around the Atlantic coast of South America. © 2013 Elsevier Ltd.