Effects of Synthesis Conditions on the Nanostructure of Hybrid Sols Produced by the Hydrolytic Condensation of (3-Methacryloxypropyl)trimethoxysilane

Polysilsesquioxanes containing methacrylate pendant groups were prepared by the sol-gel process through hydrolysis and condensation of (3-methacryloxypropyl)trimethoxysilane (MPTS) dissolved in a methanol/methyl methacrylate (MMA) mixture. The effects of different water, MMA, and methanol contents, as well as of pH, on the nanoscopic and local structures of the system, at advanced stages of the condensation reaction, were studied by small-angle X-ray scattering (SAXS) and (29)Si nuclear magnetic resonance (NMR) spectroscopy, respectively. SAXS results indicate that the nanoscopic features of the hybrid sol could be described by a hierarchical model composed of two levels, namely (i) silsesquioxane (SSQO) nanoparticles Surrounded by the methacrylate pendant groups and the methanol/MMA mixture. and (ii) aggregation zones or islands containing correlated SSQO nanoparticles, embedded in the liquid medium. The (29)Si NMR results Show that the inner Structures of SSQO nanoparticles produced at pH 1 and 3 were built Up of polyhedral structures. mainly cagelike octamers and small linear oligomers, respectively. Irrespective of MMA and methanol contents, for a [H(2)O]/[MPTS] ratio higher than or equal to 1, the SSQO nailoparticles produced at pH I exhibit an average condensation degree (CD approximate to 69-87%) and average radius of gyration (R(g) approximate to 2.5 angstrom) larger than those produced at pH 3 (CD approximate to 48-67% and R(g) approximate to 1.5 angstrom). Methanol appears to act as a redispersion agent, by decreasing the number of particles inside the aggregation zones, while the addition of MMA induces a swelling of the aggregation zones.

DMSO-Induced Denaturation of Hen Egg White Lysozyme

We report on the size, shape, structure, and interactions of lysozyme in the ternary system lysozyme/DMSO/water at low protein concentrations. Three structural regimes have been identified, which we term the ""folded"" (0 < phi(DMSO) < 0.7), ""unfolded"" (0.7 <= phi(DMSO) < 0.9), and ""partially collapsed"" (0.9 <= phi(DMSO) < 1.0) regime. Lysozyme resides in a folded conformation with an average radius of gyration of 1.3 +/- 0.1 nm for phi(DMSO) < 0.7 and unfolds (average R(g) of 2.4 +/- 0.1 nm) above phi(DMSO) > 0.7. This drastic change in the protein`s size coincides with a loss of the characteristic tertiary structure. It is preceded by a compaction of the local environment of the tryptophan residues and accompanied by a large increase in the protein`s overall flexibility. In terms of secondary structure, there is a gradual loss of alpha-helix and concomitant increase of beta-sheet structural elements toward phi(DMSO) = 0.7, while an increase in phi(DMSO) at even higher DMSO volume fractions reduces the presence of both a-helix and beta-sheet secondary structural elements. Protein-protein interactions remain overall repulsive for all values of phi(DMSO) An attempt is made to relate these structural changes to the three most important physical mechanisms that underlie them: the DMSO/water microstructure is strongly dependent on the DMSO volume fraction, DMSO acts as a strong H-bond acceptor, and DMSO is a bad solvent for the protein backbone and a number of relatively polar side groups, but a good solvent for relatively apolar side groups, such as tryptophan.

Synthesis, characterization and spectroscopic investigation of new tetrakis(acetylacetonato)thulate(III) complexes containing alkaline metals as countercations

In this work a series of tetrakis complexes C[Tm(acac)(4)] where C(+) = Li(+) Na(+) and K(+) countercations and acac = acetylacetonate ligand were synthesized and characterized for photoluminescence investigation The relevant aspect is that these complexes are water-free in the first coordination sphere The emission spectra of the tetrakis Tm(3+)-complexes present narrow bands characteristic of the (1)G(4)->(3)H(6) (479 nm) (1)G(4)->(3)F(4) (650 nm) and (1)G(4) ->(3)H(5) (779 nm) transitions of the Tm(3+) ion with the blue emission color at 479 nm as the most prominent one The lifetime values (tau) of the emitting (1)G(4) level of the C[Tm(acac)(4)] complexes were 344 360 and 400 ns for the Li(+) Na(+) and K(+) countercations respectively showing an increasing linear behavior versus the ionic radius of the alkaline ion An efficient intramolecular energy transfer process from the triplet state (T) of the ligands to the emitting (1)G(4) state of the Tm(3+) ion is observed This fact together with the absence of water molecules in first coordination sphere allows these tetrakis Tm(3+)-complexes to act as efficient blue light conversion molecular devices (c) 2010 Elsevier B V All rights reserved

Wind Power Suitability Analysis for the Gulf of Maine

This map shows one option for a viable energy source that is clean, free and endless: wind power. This map shows that the coast of Maine has the potential space and wind speed to be a location for wind farms. Four NOAA buoys placed in different locations along the Maine coast are the source of the wind speed data for this project. The average wind speed of every ten minutes of every day for the year 2004 were averaged so that each buoy was represented by one number of wind speed measured in meters/ second. The values in between these four buoys were estimated, or interpolated, using ArcGIS. Other factors that I took into consideration during this lab were distance from airports (no wind farm can be with in a three mile radius of an airport ) and distance from counties (no one wants an offshore wind farm that obstructs their view). I calculated the most appropriate locations for a wind farm in ArcGIS, by adding these three layers. The final output shows an area along Mt. Desert to be the most appropriate for development.

SEDIMENT BIOTURBATION POTENTIAL of UCA RAPAX and UCA URUGUAYENSIS AS A RESULT of THEIR FEEDING ACTIVITY

Bioturbation of mangrove sediments by Uca uruguayensis (Nobili, 1901) and U. rapax (Smith, 1870) was compared based on the grain-size composition and organic content in surface sediment around the burrow and feeding pellets in two mangrove zones of the Sao Vicente Estuary, state of São Paulo, Brazil. For each species, 25 burrows with active crabs were selected. All pellets within a 15-cm radius of each burrow were carefully collected; samples of substrate were taken; and the crab occupant was excavated, sexed, and measured for carapace width (CW). The number of spoon-tipped setae on the second maxilliped of each species was estimated; U. uruguayensis showed more of these setae than U. rapax. For both species, the sediment post-processed by feeding activity (feeding pellets) showed a similar increase of coarser fractions and a smaller organic content. However. U. uruguayensis was more efficient in removing organic matter (88.1%) from the sediment than U. rapax (37.5%). These results suggest that different numbers of spoon-tipped setae on the second maxillipeds of the fiddler crabs do not affect the potential for grain-size selection, but result in differing abilities to remove organic matter from the sediment.

Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

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

On the stability of the satellites of asteroid 87 Sylvia

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

Effect of Drilling Technique on the Early Integration of Plateau Root Form Endosteal Implants: An Experimental Study in Dogs

Purpose: This study tested the hypothesis that early integration of plateau root form endosseous implants is significantly affected by surgical drilling technique.Materials and Methods: Sixty-four implants were bilaterally placed in the diaphysial radius of 8 beagles and remained 2 and 4 weeks in vivo. Half the implants had an alumina-blasted/acid-etched surface and the other half a surface coated with calcium phosphate. Half the implants with the 2 surface types were drilled at 50 rpm without saline irrigation and the other half were drilled at 900 rpm under abundant irrigation. After euthanasia, the implants in bone were nondecalcified and referred for histologic analysis. Bone-to-implant contact, bone area fraction occupancy, and the distance from the tip of the plateau to pristine cortical bone were measured. Statistical analyses were performed by analysis of variance at a 95% level of significance considering implant surface, time in vivo, and drilling speed as independent variables and bone-to-implant contact, bone area fraction occupancy, and distance from the tip of the plateau to pristine cortical bone as dependent variables.Results: The results showed that both techniques led to implant integration and intimate contact between bone and the 2 implant surfaces. A significant increase in bone-to-implant contact and bone area fraction occupancy was observed as time elapsed at 2 and 4 weeks and for the calcium phosphate-coated implant surface compared with the alumina-blasted/acid-etched surface.Conclusions: Because the surgical drilling technique did not affect the early integration of plateau root form implants, the hypothesis was refuted. (C) 2011 American Association of Oral and Maxillofacial Surgeons J Oral Maxillofac Surg 69: 2158-2163, 2011

Characterization of Five Different Implant Surfaces and Their Effect on Osseointegration: A Study in Dogs

Background: Chemical modification of implant surface is typically associated with surface topographic alterations that may affect early osseointegration. This study investigates the effects of controlled surface alterations in early osseointegration in an animal model.Methods: Five implant surfaces were evaluated: 1) alumina-blasting, 2) biologic blasting, 3) plasma, 4) microblasted resorbable blasting media (microblasted RBM), and 5) alumina-blasting/acid-etched (AB/AE). Surface topography was characterized by scanning electron microscopy and optical interferometry, and chemical assessment by x-ray photoelectron spectroscopy. The implants were placed in the radius of six dogs, remaining 2 and 4 weeks in vivo. After euthanization, specimens were torqued-to-interface failure and non-decalcified - processed for histomorphologic bone-implant contact, and bone area fraction-occupied evaluation. Statistical evaluation was performed by one-way analysis of variance (P < 0.05) and post hoc testing by the Tukey test.Results: The alumina-blasting surface presented the highest average surface roughness and mean root square of the surface values, the biologic blasting the lowest, and AB/AE an intermediate value. The remaining surfaces presented intermediate values between the biologic blasting and AB/AE. The x-ray photoelectron spectroscopy spectra revealed calcium and phosphorus for the biologic blasting and microblasted RBM surfaces, and the highest oxygen levels for the plasma, microblasted RBM, and AB/AE surfaces. Significantly higher torque was observed at 2 weeks for the microblasted RBM surface (P < 0.04), but no differences existed between surfaces at 4 weeks (P > 0.74). No significant differences in bone-implant contact and bone area fraction-occupied values were observed at 2 and 4 weeks.Conclusion: The five surfaces were osteoconductive and resulted in high degrees of osseointegration and biomechanical fixation. J Periodontol 2011;82:742-750.

Synergistic effect in the catalytic activity of lipase Rhizomucor miehei immobilized on zeolites for the production of biodiesel

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

Crystallization and preliminary crystallographic analysis of SMase I, a sphingomyelinase from Loxosceles laeta spider venom

SMase I, a 32 kDa sphingomyelinase found in Loxosceles laeta venom, is responsible for the major pathological effects of spider envenomation. This toxin has been cloned and functionally expressed as a fusion protein containing a 6 x His tag at its N-terminus to yield a 33 kDa protein [Fernandes-Pedrosa et al. (2002), Biochem. Biophys. Res. Commun. 298, 638 - 645]. The recombinant protein possesses all the biological properties ascribed to the whole L. laeta venom, including dermonecrotic and complement-dependent haemolytic activities. Dynamic light-scattering experiments conducted at 291 K demonstrate that the sample possesses a monomodal distribution, with a hydrodynamic radius of 3.57 nm. L. laeta SMase I was crystallized by the hanging-drop vapour-diffusion technique using the sparse-matrix method. Single crystals were obtained using a buffer solution consisting of 0.08 M HEPES and 0.9 M trisodium citrate, which was titrated to pH 7.5 using 0.25 M sodium hydroxide. Complete three-dimensional diffraction data were collected to 1.8 Angstrom at the Laboratorio Nacional de Luz Sincrotron (LNLS, Campinas, Brazil). The crystals belong to the hexagonal system ( space group P6(1) or P6(5)), with unit-cell parameters a = b = 140.6, c = 113.6 Angstrom. A search for heavy-atom derivatives has been initiated and elucidation of the crystal structure is currently in progress.

Thermodynamic analysis of a non linear lattice

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

Effect of an impulsive force on vortices in a rotating Bose-Einstein condensate

The effects of a sudden increase and decrease of the interatomic interaction and harmonic-oscillator trapping potential on vortices in a quasi two-dimensional rotating Bose-Einstein condensate are investigated using the mean-field Gross-Pitaevskii equation. We also study the decay of vortices when the rotation of the condensate is suddenly stopped. Upon a free expansion of a rotating BEC with vortices the radius of the vortex core increases more rapidly than the radius of the condensate. (C) 2002 Elsevier B.V. B.V. All rights reserved.

SPH simulations of clumps formation by dissipative collision of molecular clouds - I. Non magnetic case

Computer experiments of interstellar cloud collisions were performed with a new smoothed-particle-hydrodynamics (SPH) code. The SPH quantities were calculated by using spatially adaptive smoothing lengths and the SPH fluid equations of motion were solved by means of a hierarchical multiple time-scale leapfrog. Such a combination of methods allows the code to deal with a large range of hydrodynamic quantities. A careful treatment of gas cooling by H, H(2), CO and H II, as well as a heating mechanism by cosmic rays and by H(2) production on grains surface, were also included in the code. The gas model reproduces approximately the typical environment of dark molecular clouds. The experiments were performed by impinging two dynamically identical spherical clouds onto each other with a relative velocity of 10 km s(-1) but with a different impact parameter for each case. Each object has an initial density profile obeying an r(-1)-law with a cutoff radius of 10 pc and with an initial temperature of 20 K. As a main result, cloud-cloud collision triggers fragmentation but in expense of a large amount of energy dissipated, which occurred in the head-on case only. Off-center collision did not allow remnants to fragment along the considered time (similar to 6 Myr). However, it dissipated a considerable amount of orbital energy. Structures as small as 0.1 pc, with densities of similar to 10(4) cm(-3), were observed in the more energetic collision.

Structure and Growth Kinetics of 3-Glycidoxypropyltrimethoxysilane-Derived Organic/Silica Hybrids at Different Temperatures

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