Modified silicas covalently bounded to 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrinato iron(III): synthesis, spectroscopic and EPR characterization. Catalytic studies

In this work we have studied cyclooctene epoxidation with PhIO, using a new iron porphyrin, 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrinato iron(III), supported on silica matrices via eletrostatic interaction and / or covalent bonds as catalyst. These catalysts were obtained and immobilized on the solid supports propyltrimethylammonium silica (SiN+); propyltrimethylammonium and propylimidazole silica [SiN+(IPG)] and chloropropylsilica (CPS) via elestrostatic interactions and covalent binding. Characterization of the supported catalysts by UV-Vis spectroscopy and EPR (Electron paramagnetic resonance) indicated the presence of a mixture of FeII and FeIII species in all of the three obtained catalysts. In the case of (Z)-cyclooctene epoxidation by PhIO the yields observed for cis-epoxycyclooctane were satisfactory for the reactions catalyzed by the three materials (ranging from 68% to 85%). Such results indicate that immobilization of metalloporphyrins onto solid supports via groups localized on the ortho positions of their mesophenyl rings can lead to efficient catalysts for epoxidation reactions. The catalyst 1-CPS is less active than 1-SiN and 1-SiN(IPG), this argues in favour of the immobilization of this metalloporphyrin onto solids via electrostatic interactions, which is easier to achieve and results in more active oxidation catalysts. Interestingly, the activity of the supported catalysts remained the same even after three successive recyclings; therefore, they are stable under the oxidizing conditions.

Parametric model for the analysis of concrete expansion due to alkali-aggregate reaction

The alkali-aggregate reaction (AAR) is a chemical reaction that provokes a heterogeneous expansion of concrete and reduces important properties such as Young's modulus, leading to a reduction in the structure's useful life. In this study, a parametric model is employed to determine the spatial distribution of the concrete expansion, combining normalized factors that influence the reaction through an AAR expansion law. Optimization techniques were employed to adjust the numerical results and observations in a real structure. A three-dimensional version of the model has been implemented in a finite element commercial package (ANSYS(C)) and verified in the analysis of an accelerated mortar test. Comparisons were made between two AAR mathematical descriptions for the mechanical phenomenon, using the same methodology, and an expansion curve obtained from experiment. Some parametric studies are also presented. The numerical results compared very well with the experimental data validating the proposed method.

CHARACTERIZATION OF MICROSATELLITE LOCI IN HIMATANTHUS DRASTICUS (APOCYNACEAE), A MEDICINAL PLANT FROM THE BRAZILIAN SAVANNA

Premise of the study: We developed a new set of microsatellite markers for studying the genome of the janaguba tree, Himatanthus drasticus (Mart.) Plumel, which is used in folk medicine in northeastern Brazil. These novel markers are being used to evaluate the effect of harvesting on the genetic structure and diversity of natural populations of this species. Methods and Results: Microsatellite loci were isolated from an enriched H. drasticus genomic library. Nine primer pairs successfully amplified polymorphic microsatellite regions, with an average of 8.5 alleles per locus. The average values of observed and expected heterozygosity were 0.456 and 0.601, respectively. Conclusions: The microsatellite markers described here are valuable tools for population genetics studies of H. drasticus. The majority of the primers also amplified sequences in the genome of another species of the same genus. This new set of markers may be useful in designing a genetic conservation strategy and a sustainable management plan for the species.

Changes in integument structure during the imaginal molt of the honey bee

The changing pattern of developing cuticle and associated epidermis is described during the imaginal molt in the honey bee. Observations began immediately after the pupal molt, and included histological analyses of the integument during apolysis and the subsequent deposition and differentiation of the adult cuticle. Apolysis coincides with a marked increase in the thickness and reorganization of the epidermal layer, reflecting changes in cell structure. The epidermis remains thickened during the period of cuticle deposition, suggesting intense biosynthetic activity, but turns into a very thin layer during cuticle differentiation, clearly indicating that secretory activity for cuticle formation is terminating. The thoracic cuticle differentiates earlier and becomes thicker than the abdominal. The observed changes in integument structure provide insights that permit an improved physiological characterization for staging pupal and pharate adult development.

Inferences of evolutionary and ecological events that influenced the population structure of Plebeia remota, a stingless bee from Brazil

The present study characterised the population genetic structure of Plebeia remota through mitochondrial DNA (mtDNA) analysis and evaluated evolutionary and ecological processes that may have contributed to the species current genetic scenario. Seventy feral nests were sampled representing four geographic regions (Cunha, Curitiba, Prudentopolis, and Blumenau). Fifteen composite mtDNA haplotypes were determined and a high genetic structure was detected among all populations. The current population structure may be a result of queen philopatry and vegetation shifts caused by palaeoclimatic changes and uplift of Brazilian coastal ranges. Finally, this study strongly suggests a revision of the taxonomic status of P. remota from the Prudentopolis region.

The Function and Three-Dimensional Structure of a Thromboxane A(2)/Cysteinyl Leukotriene-Binding Protein from the Saliva of a Mosquito Vector of the Malaria Parasite

The highly expressed D7 protein family of mosquito saliva has previously been shown to act as an anti-inflammatory mediator by binding host biogenic amines and cysteinyl leukotrienes (CysLTs). In this study we demonstrate that AnSt-D7L1, a two-domain member of this group from Anopheles stephensi, retains the CysLT binding function seen in the homolog AeD7 from Aedes aegypti but has lost the ability to bind biogenic amines. Unlike any previously characterized members of the D7 family, AnSt-D7L1 has acquired the important function of binding thromboxane A(2) (TXA(2)) and its analogs with high affinity. When administered to tissue preparations, AnSt-D7L1 abrogated Leukotriene C(4) (LTC(4))-induced contraction of guinea pig ileum and contraction of rat aorta by the TXA(2) analog U46619. The protein also inhibited platelet aggregation induced by both collagen and U46619 when administered to stirred platelets. The crystal structure of AnSt-D7L1 contains two OBP-like domains and has a structure similar to AeD(7). In AnSt-D7L1, the binding pocket of the C-terminal domain has been rearranged relative to AeD7, making the protein unable to bind biogenic amines. Structures of the ligand complexes show that CysLTs and TXA(2) analogs both bind in the same hydrophobic pocket of the N-terminal domain. The TXA(2) analog U46619 is stabilized by hydrogen bonding interactions of the omega-5 hydroxyl group with the phenolic hydroxyl group of Tyr 52. LTC(4) and occupies a very similar position to LTE(4) in the previously determined structure of its complex with AeD7. As yet, it is not known what, if any, new function has been acquired by the rearranged C-terminal domain. This article presents, to our knowledge, the first structural characterization of a protein from mosquito saliva that inhibits collagen mediated platelet activation.

Characterization of subgraph relationships and distribution in complex networks

A network can be analyzed at different topological scales, ranging from single nodes to motifs, communities, up to the complete structure. We propose a novel approach which extends from single nodes to the whole network level by considering non-overlapping subgraphs (i.e. connected components) and their interrelationships and distribution through the network. Though such subgraphs can be completely general, our methodology focuses on the cases in which the nodes of these subgraphs share some special feature, such as being critical for the proper operation of the network. The methodology of subgraph characterization involves two main aspects: (i) the generation of histograms of subgraph sizes and distances between subgraphs and (ii) a merging algorithm, developed to assess the relevance of nodes outside subgraphs by progressively merging subgraphs until the whole network is covered. The latter procedure complements the histograms by taking into account the nodes lying between subgraphs, as well as the relevance of these nodes to the overall subgraph interconnectivity. Experiments were carried out using four types of network models and five instances of real-world networks, in order to illustrate how subgraph characterization can help complementing complex network-based studies.

CHARACTERIZATION OF EXPONENTIAL DIVERGENCE OF THE KALMAN FILTER FOR TIME-VARYING SYSTEMS

This paper studies semistability of the recursive Kalman filter in the context of linear time-varying (LTV), possibly nondetectable systems with incorrect noise information. Semistability is a key property, as it ensures that the actual estimation error does not diverge exponentially. We explore structural properties of the filter to obtain a necessary and sufficient condition for the filter to be semistable. The condition does not involve limiting gains nor the solution of Riccati equations, as they can be difficult to obtain numerically and may not exist. We also compare semistability with the notions of stability and stability w.r.t. the initial error covariance, and we show that semistability in a sense makes no distinction between persistent and nonpersistent incorrect noise models, as opposed to stability. In the linear time invariant scenario we obtain algebraic, easy to test conditions for semistability and stability, which complement results available in the context of detectable systems. Illustrative examples are included.

Unraveling effects of disorder on the electronic structure of SiO(2) from first principles

We present a first-principles systematic study of the electronic structure of SiO(2) including the crystalline polymorphs alpha quartz and beta cristobalite, and different types of disorder leading to the amorphous phase. We start from calculations within density functional theory and proceed to more sophisticated quasiparticle calculations according to the GW scheme. Our results show that different origins of disorder have also different impact on atomic and electronic-density fluctuations, which affect the electronic structure and, in particular, the size of the mobility gap in each case.

Characterization of Yeast Extracellular Vesicles: Evidence for the Participation of Different Pathways of Cellular Traffic in Vesicle Biogenesis

Background: Extracellular vesicles in yeast cells are involved in the molecular traffic across the cell wall. In yeast pathogens, these vesicles have been implicated in the transport of proteins, lipids, polysaccharide and pigments to the extracellular space. Cellular pathways required for the biogenesis of yeast extracellular vesicles are largely unknown. Methodology/Principal Findings: We characterized extracellular vesicle production in wild type (WT) and mutant strains of the model yeast Saccharomyces cerevisiae using transmission electron microscopy in combination with light scattering analysis, lipid extraction and proteomics. WT cells and mutants with defective expression of Sec4p, a secretory vesicle-associated Rab GTPase essential for Golgi-derived exocytosis, or Snf7p, which is involved in multivesicular body (MVB) formation, were analyzed in parallel. Bilayered vesicles with diameters at the 100-300 nm range were found in extracellular fractions from yeast cultures. Proteomic analysis of vesicular fractions from the cells aforementioned and additional mutants with defects in conventional secretion pathways (sec1-1, fusion of Golgi-derived exocytic vesicles with the plasma membrane; bos1-1, vesicle targeting to the Golgi complex) or MVB functionality (vps23, late endosomal trafficking) revealed a complex and interrelated protein collection. Semi-quantitative analysis of protein abundance revealed that mutations in both MVB- and Golgi-derived pathways affected the composition of yeast extracellular vesicles, but none abrogated vesicle production. Lipid analysis revealed that mutants with defects in Golgi-related components of the secretory pathway had slower vesicle release kinetics, as inferred from intracellular accumulation of sterols and reduced detection of these lipids in vesicle fractions in comparison with WT cells. Conclusions/Significance: Our results suggest that both conventional and unconventional pathways of secretion are required for biogenesis of extracellular vesicles, which demonstrate the complexity of this process in the biology of yeast cells.

EBSD characterization of an ECAP deformed Nb single crystal

A niobium single crystal was subjected to equal channel angular pressing (ECAP) at room temperature after orienting the crystal such that [1 -1 -1] ayen ND, [0 1 -1] ayen ED, and [-2 -1 -1] ayen TD. Electron backscatter diffraction (EBSD) was used to characterize the microstructures both on the transverse and the longitudinal sections of the deformed sample. After one pass of ECAP the single crystal exhibits a group of homogeneously distributed large misorientation sheets and a well formed cell structure in the matrix. The traces of the large misorientation sheets match very well with the most favorably oriented slip plane and one of the slip directions is macroscopically aligned with the simple shear plane. The lattice rotation during deformation was quantitatively estimated through comparison of the orientations parallel to three macroscopic axes before and after deformation. An effort has been made to link the microstructure with the initial crystal orientation. Collinear slip systems are believed to be activated during deformation. The full constraints Taylor model was used to simulate the orientation evolution during ECAP. The result matched only partially with the experimental observation.

Crystallographic characterization of silicon nitride ceramics sintered with Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) additions

Silicon nitride ceramics were sintered using Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) (E(2)O(3) denotes a mixed oxide Of Y(2)O(3) and rare-earth oxides) as sintering additives. The intergranular phases formed after sintering was investigated using high-resolution X-ray diffraction (HRXRD). The use of synchrotron radiation enabled high angular resolution and a high signal to background ratio. Besides the appearance Of beta-Si(3)N(4) phase the intergranular phases Y(3)Al(5)O(12) (YAG) and Y(2)SiO(5) were identified in both samples. The refinement of the structural parameters by the Rietveld method indicated similar crystalline structure Of beta-Si(3)N(4) for both systems used as sintering additive. On the other hand, the intergranular phases Y(3)Al(5)O(12) and Y(2)SiO(5) shown a decrease of the lattice parameters, when E(2)O(3) was used as additive, indicating the formation of solid solutions of E(3)Al(5)O(12) and E(2)SiO(5), respectively. (C) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Manufacture and characterization of ultra and microfiltration ceramic membranes by isostatic pressing

This paper describes the manufacture of tubular UF and MF porous and supported ceramic membranes to oil/water emulsions demulsification. For such a purpose, a rigorous control was realized over the distribution and size of pores. Suspensions at 30 vol.% of solids (zirconia or alumina powder and sucrose) and 70 vol.% of liquids (isopropyl alcohol and PVB) were prepared in a jar mill varying the milling time of the sucrose particles, according to the pores size expected. The membranes were prepared by isostatic pressing method and structurally characterized by SEM, porosimetry by mercury intrusion and measurements of weight by immersion. The morphological characterization of the membranes identified the formation of porous zirconia and alumina membranes and supported membranes. The results of porosimetry analysis by mercury intrusion presented an average pore size of 1.8 mu m for the microfiltration porous membranes and for the ultrafiltration supported membranes, pores with average size of 0.01-0.03 mu m in the top-layer and 1.8 mu m in the support. By means of the manufacture method applied, it was possible to produce ultra and microfiltration membranes with high potential to be applied to the separation of oil/water emulsions. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Molecular characterization of a miraculin-like gene differentially expressed during coffee development and coffee leaf miner infestation

The characterization of a coffee gene encoding a protein similar to miraculin-like proteins, which are members of the plant Kunitz serine trypsin inhibitor (STI) family of proteinase inhibitors (PIs), is described. PIs are important proteins in plant defence against insects and in the regulation of proteolysis during plant development. This gene has high identity with the Richadella dulcifica taste-modifying protein miraculin and with the tomato protein LeMir; and was named as CoMir (Coffea miraculin). Structural protein modelling indicated that CoMir had structural similarities with the Kunitz STI proteins, but suggested specific folding structures. CoMir was up-regulated after coffee leaf miner (Leucoptera coffella) oviposition in resistant plants of a progeny derived from crosses between C. racemosa (resistant) and C. arabica (susceptible). Interestingly, this gene was down-regulated during coffee leaf miner herbivory in susceptible plants. CoMir expression was up-regulated after abscisic acid application and wounding stress and was prominent during the early stages of flower and fruit development. In situ hybridization revealed that CoMir transcripts accumulated in the anther tissues that display programmed cell death (tapetum, endothecium and stomium) and in the metaxylem vessels of the petals, stigma and leaves. In addition, the recombinant protein CoMir shows inhibitory activity against trypsin. According to the present results CoMir may act in proteolytic regulation during coffee development and in the defence against L. coffeella. The similarity of CoMir with other Kunitz STI proteins and the role of CoMir in plant development and plant stress are discussed.

Topology Optimized Design, Microfabrication and Characterization of Electro-Thermally Driven Microgripper

This article presents a systematic and logical study of the topology optimized design, microfabrication, and static/dynamic performance characterization of an electro-thermo-mechanical microgripper. The microgripper is designed using a topology optimization algorithm based on a spatial filtering technique and considering different penalization coefficients for different material properties during the optimization cycle. The microgripper design has a symmetric monolithic 2D structure which consists of a complex combination of rigid links integrating both the actuating and gripping mechanisms. The numerical simulation is performed by studying the effects of convective heat transfer, thermal boundary conditions at the fixed anchors, and microgripper performance considering temperature-dependent and independent material properties. The microgripper is fabricated from a 25 mm thick nickel foil using laser microfabrication technology and its static/dynamic performance is experimentally evaluated. The static and dynamic electro-mechanical characteristics are analyzed as step response functions with respect to tweezing/actuating displacements, applied current/power, and actual electric resistance. A microgripper prototype having overall dimensions of 1mm (L) X 2.5mm (W) is able to deliver the maximum tweezing and actuating displacements of 25.5 mm and 33.2 mm along X and Y axes, respectively, under an applied power of 2.32 W. Experimental performance is compared with finite element modeling simulation results.