Direct electron paramagnetic resonance monitoring of the peptide synthesis coupling reaction in polymeric support

This work demonstrates, for the first time. a time-resolved electron paramagnetic resonance (EPR) monitoring of a chemical reaction occurring in a polymeric structure. The progress of the coupling of a N-alpha-tert-butyloxycarbonyl-2.2.6.6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (Boc-TOAC) spin probe to a model peptide-resin was followed through EPR spectra. Progressive line broadening of EPR peaks was observed, indicative of an increased population of immobilized spin probe molecules attached to the solid support. The time for spectral stabilization of this process coincided with that determined in a previous Coupling study. thereby validating this in situ quantitative monitoring of the reaction. In addition, the influence of polymer swelling degree and solvent viscosity, as well as of the steric hindrance within beads. on the rate of coupling reaction was also addressed. A deeper evaluation of the latter effect was possible by determining unusual polymer parameters such as the average site-site distance and site-concentration within resin beads in each solvent system. (c) 2006 Elsevier Ltd. All rights reserved.

Fine structure of the boundary tissue of the seminiferous tubuli of the vampire bat (Desmodus rotundus, G.; Microchiroptera).

Structurally the boundary tissue of the vampire bat seminiferous tubuli showed 2 to 5 layers of connective tissue in which elongated contractile cells and lamellar and/or fibrillar collagen were noticed. This boundary tissue forms the seminiferous tubular lamina propria. Its structure was more complex around the seminiferous tubuli near the Capsula testicularis than between the adjacent and contiguous tubuli into the testicular lobuli. The whole ultrastructural organization of the seminiferous lamina propria was described here.

Genetic structure of populations of Rhizoctonia solani AG-3 on potato in eastern North Carolina

A polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) method was developed to identify and differentiate genotypes of Rhizoctonia solani anastomosis group 3 subgroup PT (AG-3 PT), a fungal pathogen of potato. Polymorphic co-dominant single-locus PCR-RFLP markers were identified after sequencing of clones from a genomic library and digestion with restriction enzymes. Multilocus genotypes were determined by a combination of PCR product and digestion with a specific restriction enzyme for each of seven loci. A sample of 104 isolates from one commercial field in each of five counties in eastern North Carolina was analyzed, and evidence for high levels of gene flow between populations was revealed. When data were clone-corrected and samples pooled into one single North Carolina population, random associations of alleles were found for all loci or pairs of loci, indicating random mating. However, when all genotypes were analyzed, the observed genotypic diversity deviated from panmixia and alleles within and between loci were not randomly associated. These findings support a model of population structure for R. solani AG-3 PT on potato that includes both recombination and clonality.

Structure and properties of Ti4+-Ureasil organic-inorganic hybrids

Hybrid planar waveguides were prepared from Ti4+-acetylacetone (acac)-Ureasil sols deposited on glass substrates. Structural features have been investigated by spectroscopic measurements (Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Raman scattering) and Small Angle X-ray Scattering (SAXS). Addition of Ti 4+-acac to the ureasil (Ti:Si molar ratio 1:1) leads to the formation of bonds between the Ti complex and the siloxane groups, whereas further addition of Ti4+ (Ti:Si molar ratio 5:1) leads to the additional formation of titanium-rich nanoclusters. The optical parameters of the waveguides such as refractive index, thickness, propagating modes and attenuation coefficient were measured at 632.8, 543.5 and 1550 nm by the prism coupling technique. The refractive index can be tuned by the Ti4+ relative content. The few microns thick planar waveguides support well confined propagating modes with low attenuation loss for all compositions. ©2006 Sociedade Brasileira de Química.

A metabolic pathway assembled by enzyme selection may support herbivory of leaf-cutter ants on plant starch

Mutualistic associations shape the evolution in different organism groups. The association between the leaf-cutter ant Atta sexdens and the basidiomycete fungus Leucoagaricus gongylophorus has enabled them to degrade starch from plant material generating glucose, which is a major food source for both mutualists. Starch degradation is promoted by enzymes contained in the fecal fluid that ants deposit on the fungus culture in cut leaves inside the nests. To understand the dynamics of starch degradation in ant nests, we purified and characterized starch degrading enzymes from the ant fecal fluid and from laboratory cultures of L. gongylophorus and found that the ants intestine positively selects fungal α-amylase and a maltase likely produced by the ants, as a negative selection is imposed to fungal maltase and ant α-amylases. Selected enzymes are more resistant to catabolic repression by glucose and proposed to structure a metabolic pathway in which the fungal α-amylase initiates starch catalysis to generate byproducts which are sequentially degraded by the maltase to produce glucose. The pathway is responsible for effective degradation of starch and proposed to represent a major evolutionary innovation enabling efficient starch assimilation from plant material by leaf-cutters. © 2013 Elsevier Ltd.

Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion

The effect of amorphous (am-), monoclinic (m-), and tetragonal (t-) ZrO2 phase on the physicochemical and catalytic properties of supported Cu catalysts for ethanol conversion was studied. The electronic parameters of Cu/ZrO2 were determined by in situ XAS, and the surface properties of Cu/ZrO2 were defined by XPS and DRIFTS of CO-adsorbed. The results demonstrated that the kind of ZrO2 phase plays a key role in the determination of structure and catalytic properties of Cu/ZrO 2 catalysts predetermined by the interface at Cu/ZrO2. The electron transfer between support and Cu surface, caused by the oxygen vacancies at m-ZrO2 and am-ZrO2, is responsible for the active sites for acetaldehyde and ethyl acetate formation. The highest selectivity to ethyl acetate for Cu/m-ZrO2 catalyst up to 513 K was caused by the optimal ratio of Cu0/Cu+ species and the high density of basic sites (O2-) associated with the oxygen mobility from the bulk m-ZrO2. © 2013 Elsevier Inc. All rights reserved.

Genetic Structure of Lutzomyia longipalpis Populations in Mato Grosso Do Sul, Brazil, Based on Microsatellite Markers

Background:Lutzomyia longipalpis (Diptera: Psychodidae) is the major vector of Leishmania (Leishmania) infantum and thus plays a crucial role in the epidemiology of American visceral leishmaniasis (AVL). This vector is the best studied species of sand fly in the Neotropical region. Many studies claim that this vector is in fact a species complex; however there is still no consensus regarding the number of species that belong into this complex or the geographical distribution of sibling species. The aim of the present study was to analyze the genetic relationships within Lu. longipalpis populations in the state of Mato Grosso do Sul (MS), Brazil.Methodology/Principal Findings:We collected 30 Lu. longipalpis (15 females and 15 males) from five localities (Campo Grande, Três Lagoas, Aquidauana, Miranda and Bonito) and 30 Lu. Cruzi from Corumbá, totaling 180 sandflies from MS, and 30 Lu. longipalpis from Estrela de Alagoas, state of Alagoas (AL), Northeast Brazil. We show that eight previously described microsatellite loci were sufficient in distinguishing Lu. longipalpis from Lu. Cruzi, which is a closely related species, and in differentiating between Lu. longipalpis collected in MS versus Estrela de Alagoas. Analyses of the genotypes revealed introgression between sympatric Lu. longipalpis and Lu. Cruzi.Conclusions/Significance:Our findings support the hypothesis of cryptic species within the Lu. longipalpis complex. Furthermore, our data revealed introgression between Lu. longipalpis and Lu. cruzi. This phenomenon should be further investigated to determine the level and incidence of hybridization between these two species. We also demonstrated that microsatellite markers are a powerful tool for differentiating sand fly populations and species. The present study has elucidated the population structure of Lu. longipalpis in MS and, by extension, the Neotropical Lu. longipalpis complex itself. © 2013 Santos et al.

Er3+-doped Y2O3 obtained by polymeric precursor: Synthesis, structure and upconversion emission properties

The relentless pursuit for materials containing rare earth ions with photoluminescent properties has led to several studies with applications in the development of new technologies. The main focus of this work is the preparation of Er3+-doped polycrystalline Y2O3 with photoluminescent properties using PEG as an organic precursor and heat-treated at different temperatures. The methodology used in this synthesis is highly attractive due to its high feasibility for improved technology and low cost for preparing materials. The behavior of the viscous resin has been evaluated and the final compounds exhibited the formation of a cubic polycrystalline phase, which is able to support variations in Er3+ doping concentrations up to 10 mol%, without significant changes in the polycrystalline parameters. The values of the nanocrystallite size calculated by Scherrer's equation showed direct dependence on the heat-treatment temperature as well as the Er3+ concentration. Intense emission in the visible region under excitation at 980 nm was attributed to an upconversion phenomenon assigned to the intraconfigurational f-f transitions of Er3+ ions. The upconversion mechanism was investigated and it was demonstrated that the higher intense emission in the red region in comparison to the emission in the green region is related to the crystallite size. The studies about the intensity showed the dependence of upconversion emission of power source, indicating that two-photon are responsible for the green and red photoluminescence. These polycrystalline materials exhibit properties that make them promising for use in solar energy systems, C-telecom band or solid-state laser devices. (C) 2014 Elsevier B.V. All rights reserved.

Application of passive control to energy harvester efficiency using a nonideal portal frame structural support system

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

Leaf colleters in Tabernaemontana catharinensis (Apocynaceae, Rauvolfioideae): structure, ontogenesis, and cellular secretion

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

The subdomain structure of human serum albumin in solution under different pH conditions studied by small angle X-ray scattering

Small-angle X-ray scattering (SAXS) was used to study structural characteristics of human serum albumin (HSA) in solution under different pH conditions. Guinier analysis of SAXS results yielded values of the molecular radius of gyration ranging from 26.7 Å to 34.5 Å for pH varying from 2.5 to 7.0. This suggests the existence of significant differences in the overall shape of the molecule at different pH. Molecular models based on subdomains with different spatial configurations were proposed. The distance distribution functions associated with these models were calculated and compared with those determined from the experimental SAXS intensity functions. The conclusion of this SAXS study is that the arrangement of molecular subdomains is clearly pH dependent; the molecule adopting more or less compact configuration for different pH conditions. The conclusions of this systematic study on the modification in molecular shape of HSA as a response to pH changes is consistent with those of previous investigations performed for particular pH conditions.