Interactions between lipid-free apolipoprotein-AI and a lipopeptide incorporating the RGDS cell adhesion motif

The interaction of a designed bioactive lipopeptide C16-GGGRGDS, comprising a hexadecyl lipid chain attached to a functional heptapeptide, with the lipid-free apoliprotein, Apo-AI, is examined. This apolipoprotein is a major component of high density lipoprotein and it is involved in lipid metabolism and may serve as a biomarker for cardiovascular disease and Alzheimers’ disease. We find via isothermal titration calorimetry that binding between the lipopeptide and Apo-AI occurs up to a saturation condition, just above equimolar for a 10.7 μM concentration of Apo-AI. A similar value is obtained from circular dichroism spectroscopy, which probes the reduction in α-helical secondary structure of Apo-AI upon addition of C16-GGGRGDS. Electron microscopy images show a persistence of fibrillar structures due to self-assembly of C16-GGGRGDS in mixtures with Apo-AI above the saturation binding condition. A small fraction of spheroidal or possibly “nanodisc” structures was observed. Small-angle X-ray scattering (SAXS) data for Apo-AI can be fitted using a published crystal structure of the Apo-AI dimer. The SAXS data for the lipopeptide/ Apo-AI mixtures above the saturation binding conditions can be fitted to the contribution from fibrillar structures coexisting with flat discs corresponding to Apo-AI/lipopeptide aggregates.

Extensive Bilayer Perforation Coupled with the Phase Transition Region of an Anionic Phospholipid

At low ionic strength dimyristoylphosphatidylglycerol (DMPG) exhibits a broad phase transition region characterized by several superimposed calorimetric peaks. Peculiar properties, such as sample transparency, are observed only in the transition region. In this work we use differential scanning calorimetry (DSC), turbidity. and optical microscopy to study the narrowing of the transition region with the increase of ionic strength (0-500 mM NaCl). Upon addition of salt, the temperature extension of the transition region is reduced, and the number of calorimetric peaks decreases until a single cooperative event at T(m) = 23 degrees C is observed in the presence of 500 mM NaCl. The transition region is always coupled with a decrease in turbidity, but a transparent region is detected within the melting process only in the presence of up to 20 mM NaCl. The vanishing of the transparent region is associated with one of the calorimetric peaks. Optical microscopy of giant vesicles shows that bilayers first rupture when the transition region is reached and Subsequently lose optical contrast. Fluorescence microscopy reveals a blurry and undefined image in the transparent region, suggesting a different lipid self-assembly. Overall sample turbidity can be directly related to the bilayer optical contrast. Our observations are discussed in terms of the bilayer being perforated along the transition region. In the narrower temperature interval of the transparent region, dependent on the ionic strength, the perforation is extensive and the bilayer completely loses the optical contrast.

Probing the functionalization of gold surfaces and protein adsorption by PM-IRRAS

The control of morphology and coating of metal surfaces is essential for a number of organic electronic devices including photovoltaic cells and sensors. In this study, we monitor the functionalization of gold surfaces with 11-mercaptoundecanoic acid (MUA, HS(CH(2))(10)CO(2)H) and cysteamine, aiming at passivating the surfaces for application in surface plasmon resonance (SPR) biosensors. Using polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), cyclic voltammetry, atomic force microscopy and quartz crystal microbalance, we observed a time-dependent organization process of the adsorbed MUA monolayer with alkyl chains perpendicular to the gold surface. Such optimized condition for surface passivation was obtained with a systematic search for experimental parameters leading to the lowest electrochemical signal of the functionalized gold electrode. The ability to build supramolecular architectures was also confirmed by detecting with PM-IRRAS the adsorption of streptavidin on the MUA-functionalized gold. As the approaches used for surface functionalization and its verification with PM-IRRAS are generic, one may now envisage monitoring the fabrication of tailored electrodes for a variety of applications.

Novel immunoadjuvants based on cationic lipid: Preparation, characterization and activity in vivo

The interactions between three different protein antigens and dioctadecyldimethylammonium bromide (DODAB) dispersed in aqueous solutions from probe sonication or adsorbed its one bilayer onto particles was comparatively investigated. The three model proteins were bovine serum albumin (BSA), purified 18 kDa/14 kDa antigens from Taenia crassiceps (18/14-Tcra) and a recombinant, heat-shock protein hsp-18 kDa from Mycobacterium leprae. Protein-DODAB complexes in water solution were characterized by dynamic light scattering for sizing and zeta-potential analysis. Cationic complexes (80-100 nm of mean hydrodynamic diameter) displayed sizes similar to those of DODAB bilayer fragments (BF) in aqueous solution and good colloid stability over a range of DODAB and protein concentrations. The amount of cationic lipid required for attaining zero of zeta-potential at a given protein amount depended on protein nature being smaller for 18 kDa/14 kDa antigens than for BSA. Mean diameters for DODAB/protein complexes increased, whereas zeta-potentials decreased with NaCl or protein concentration. In mice, weak IgG production but significant cellular immune responses were induced by the complexes in comparison to antigens alone or carried by aluminum hydroxide as shown from IgG in serum determined by ELISA, delayed type hypersensitivity reaction from footpad swelling tests and cytokines analysis. The novel cationic adjuvant/protein complexes revealed good colloid stability and potential for vaccine design at a reduced DODAB concentration. (C) 2009 Elsevier Ltd. All rights reserved.

Photocatalyst TiO(2)-Co: the effect of doping depth profile on methylene blue degradation

In this work, we study the effect of doping depth profile on the photocatalytic and surface properties of TiO(2) films. Two thin film layers of TiO(2) (200 nm) and Co (5 nm), respectively, were deposited by physical evaporation on glass substrate. These films were annealed for 1 s at 100 and 400 A degrees C and the Co layer was removed by chemical etching. Atomic force microscopy (AFM) phase images showed changes in the surface in function of thermal treatment. The grazing-incidence X-ray fluorescence (GIXRF) measurements indicated that the thermal treatment caused migration of Co atoms to below the surface, the depths found were between 19 and 29 nm. The contact angle showed distinct values in function of the doped profile or Co surface concentration. The UV-vis spectra presented a red shift with the increasing of thermal treatment. Photocatalytical assays were performed by methylene blue discoloration and the higher activity was found for TiO(2)-Co treated at 400 A degrees C, the ESI-MS showed the fragments formed during the methylene blue decomposition.

Fatigue strength of HVOF sprayed Cr(3)C(2)-25NiCr and WC-10Ni on AISI 4340 steel

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

Craqueamento térmico e termocatalítico do óleo de girassol (Hellianthus annus L.) sobre materiais micro e mesoporosos

Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it

Evolução tectono-estrutural do Campo de Xaréu (Sub-bacia de Mundaú, Bacia do Ceará - NE do Brasil: abordagem multiescala e pluriferramental

The Xaréu Oil Field, located in the center-southern portion of the Mundaú Sub-Basin (eastern portion of the Ceará Basin), is characterized by a main Iramework of NW-trending and NE-dipping faults. The faults in the Xaréu Oil Field, among which the Xaréu Fautt stands out, are arranged according to an extensional-listriclan, rooted on a detachment surface corresponding to the Mundaú Fault, the border fautt of Mundaú Sub-Basin. During the tectonic-structural evolution of the Xaréu Oil Field and the Mundaú Sub-Basin, the Mundaú Fault played a crucial role on the control of the geometry of both compartments. The main carbonatic unit in the Xaréu Oil Field, named the Trairí Member(Paracuru Formation of Late Aptian to Early Albian age), contains the largest oil volume in the field, concentrated in structurally-controlled accumulations. The Trairí Member is composed by a variety of carbonatic rocks (massive, bedded or laminated calcilutites, ostracodites, calcarenites and carbonatic rudites, all of them presenting variable degrees of dolomitization). The carbonatic rocks are interbedded into thick packages of black shales and marls, besides local beds of siliciclastic conglomerates, sandstones, siltnes and argillites. From the spatial association and the genetic relationships between the carbonatic and siliciclastic units, it is possible to group them in three lithofacies associations (Marginal Plain, Ramp and Lacustrine Interior) that, together, were developed in a lacustrine system associated to a marginal sabkha. Structural studies based on drill coresthat sample the Trairí Member in the Xaréu Oil Field allowed to characterize two generations of meso- to microscale structures: the D1 group presents a typical hydroplastic character, being characterized by intra/interstratal to oblique-bedding shear zones. The hydroplastic character related to these structures allowed to infer their development at an early-lithilication stage of the Trairí Member, leading to infer an Early Cretaceous age to them. The second group of structures identified in the drill cores, nominated D2 and ascribed to a Neogene age, presents a strictly brttle character, being typilied by normal faults and slickenfibers of re-crystallized clayminerals, ali olthem displaying variable orientations. Although the present faults in the Xaréu Oil Field (and, consequently, in the Mundaú Sub-Basin) were classically relerred as struetures of essentially normal displacement, the kinematics analysis of the meso-to microscaie D1 struetures in the drill cores led to deline oblique displacements (normal with a clockwise strike-slip component) to these faults, indicating a main tectonic transport to ENE. These oblique movements would be responsible for the installation of a transtensive context in the Mundaú Sub-Basin, as part of the transcurrent to translormant opening of the Atlantic Equatorial Margin. The balancing of four struetural cross-sections ofthe Xaréu Oil Field indicates that the Mundaú Fault was responsible for more than 50% of the total stretching (ß factor) registered during the Early Aptian. At the initial stages of the "rifting", during Early Aptianuntil the Holocene, the Mundaú Sub-Basin (and consequently the Xaréu Oil Fleld) accumulated a total stretching between 1.21 and 1.23; in other words, the crust in this segment of the Atlantic Equatorial Margin was subjeeted to an elongation of about 20%. From estimates of oblique displacements related to the faults, it ws possible to construct diagrams that allow the determination of stretching factors related to these displacements. Using these diagrams and assuming the sense 01 dominant teetonictransport towards ENE, it was possible to calculate the real stretching lactors related to the oblique movement 0 of the faults in the Mundaú Sub-Basin. which reached actual values between 1.28 and 1.42. ln addnion to the tectonic-structural studies in the Xaréu Oil Field, the interpretation of remote sensing products, coupled wnh characterization of terrain analogues in seleeted areas along the northern Ceará State (continental margins of the Ceará and Potiguar basins), provided addnional data and constraints about the teetonic-structural evolution of the oil lield. The work at the analogue sites was particularly effective in the recognition and mapping, in semidetail scale, several generations of struetures originated under a brittle regime. Ali the obtained information (from the Xaréu Oil Field, the remote sensor data and the terrain analogues) were jointly interpreted, culminating with the proposnion of an evolutionary model lor this segment of the Atlantic Equatorial Margin; this model that can be applied to the whole Margin, as well. This segmentof the Atlantic Equatorial Margin was delormedin an early E-W (when considered lhe present-day position of the South American Plate) transcurrent to transform regime with dextral kinematics, started Irom, at least, the Early Aptian, which left its record in several outcrops along the continental margin of the Ceará State and specilically in the Xaréu off Field. The continuous operation of the regime, through the Albian and later periods, led to the definitive separation between the South American and African plates, with the formation of oceanic lithosphere between the two continental blocks, due to the emplacement off spreading centers. This process involved the subsequent transition of the transcurrent to a translorm dextral regime, creating lhe Equatorial Atlantic Oceano With the separation between the South American and African plates already completed and the increasing separation between lhe continental masses, other tecton ic mechanisms began to act during the Cenozoic (even though the Cretaceous tectonic regime lasted until the Neogene), like an E-W compressive stress líeld (related to the spreading olthe oceanic floor along lhe M id-Atlantic Ridge and to the compression of the Andean Chain) effective Irom the Late Cretaceous, and a state of general extension olthe horizontal surface (due to the thermal uplift ofthe central portion of Borborema Province), effective during the Neogene. The overlap of these mechanisms during the Cenozoic led to the imprint of a complex tectonic framework, which apparently influenced the migration and entrapment 01 hydrocarbon in the Ceará Basin

Postprandial thermogenesis in Bothrops moojeni (Serpentes: Viperidae)

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

Photoluminescence properties and synthesis of a PZT mesostructure obtained by the microwave-assisted hydrothermal method

Micro-cube-shaped lead zirconate titanate was synthesized using the microwave-assisted hydrothermal method. Photoluminescence and field emission scanning electron microscopy were used for monitoring the formation of mesocrystals. Based on these results, a growth mechanism was then proposed which involved nanoparticle aggregation, nanoplate self-assembly on specific architecture and the final formation of mesoscopic micro-cube-shaped lead zirconate titanate. (C) 2011 Elsevier B. V. All rights reserved.

Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photocatalyst TiO2-Co: the effect of doping depth profile on methylene blue degradation

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

Sol-gel synthesis of titania-alumina catalyst supports

Titanium oxide is a good candidate as new support for hydrotreating (HDT) catalysts, but has the inconvenience of presenting small surface area and poor thermal stability. To overcome these handicaps TiO2-Al2O3 mixed oxides were proposed as catalyst support. Here, the results concerning the preparation, characterization and testing of molybdenum catalyst supported on titania-alumina are presented. The support was prepared by sol-gel route using titanium and aluminum isopropoxides, chelated with acetylacetone (acac) to promote similar hydrolysis ratio for both the alcoxides. The effect of nominal complexing ratios [acac]/[Ti] and of sol aging temperature on the structural features of nanometric particles was analyzed by quasi-elastic light scattering (QELS) and N-2 adsorption isotherm measurements. These characterizations have shown that the addition of acac and the increase of aging temperature favor the full dispersion of primary nanoparticles in mother acid solution. The dried powder presents a monomodal distribution of slit-shaped micropores, formed by irregular packing of platelet primary particles, surface area superior to 200 m(2) g(-1) and mean pore size of about 1 nm. These characteristics of porous texture are preserved after firing at 673 K. The diffraction patterns of sample fired above 973 K show only the presence of anatase crystalline phase. The crystalline structure of the support remained unaltered after molybdenum adsorption, but the surface area and the micropore volume were drastically reduced. (C) 2002 Published by Elsevier B.V. B.V.

Dichloro(cyclohexilidene-1-methylene)(phenyl)Te(IV). Looking for the theoretical treatment

C(13)H(16)Cl(2)Te,M(r)=370.76,P2(1)/a, a = 8.1833(8), b = 8.4163(8), c = 20.787(2) A, beta = 99.52(1)degrees, Z = 4, R(1) = 0,0275. The primary coordination around the Te(IV) atom is consistent with a pseudo-trigonal bipyramidal bond configuration with two Cl atoms occupying axial positions while the C atoms and the lone pair of electrons occupy the equatorial positions. The Te(IV) atom is involved in an intermolecular secondary interaction resulting in the self assembly of zigzag-chains supramolecular array. In order to determine the theoretical basis set for the Te atom which leads to the best agreement with the experimental data, a large series of geometry optimizations were performed on dichloro dimethyl Te(IV), as a model compound, and the results compared with the mean distances and angles obtained from 45 X-ray structures. The Ahlrichs basis set plus the Hay & Wadt ECP was selected and used for a series of calculations performed on the title compound.

Supramolecular assemblies of cis-palladium complexes dominated by C-H center dot center dot center dot Cl interactions

Two cis-related palladium(II) complexes [PdCl(2)(PPh(3))(tu)] (1) and [PdCl(2)(tmen)] (2) {PPh(3) = triphenylphosphine, tu = thiourea, tmen = N,N,N,N-tetramethylethylenediamine} have been synthesized and characterized by elemental analysis, IR and NMR spectroscopies, and single crystal X-ray diffraction. In 1, N-H center dot center dot center dot Cl hydrogen bonds are responsible for the formation of a dimer which connects to an adjacent one through weak C-H center dot center dot center dot Cl interactions, yielding 1D tapes. The crystal packing of compound 2 consists of zigzag ribbons of [PdCl(2)(tmen)] self-assembled by C-H center dot center dot center dot Cl hydrogen bonds which also holds the chains together, giving rise to a 2D layered structure. (C) 2006 Elsevier B.V. All rights reserved.