Electrode surface modifications improve cathode hydrogen production and anode capacity in Ni-MH batteries

This paper reports results from electrochemical evaluations of electrodes used as cathodes for a hydrogen evolution reaction and anodes in Ni-MH batteries that had been surface-modified by micro-encapsulation, co-deposition and sol-gel methods. The surface modifications produced actual improvements in the corresponding electrochemical reactions by enhancing the performance and/or the mechanical stability of the electrode material. (c) 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Utilização de uma matriz híbrida orgânica-inorgânica na dinâmica de liberação controlada de fármacos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Efeito de diferentes soluções de clorexidina na produção e estabilidade mecânica da união resina-dentina afetada por cárie

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Um estudo da estabilidade mecânica de poços a partir de perfis geofísicos em formações pouco consolidadas

A análise da estabilidade mecânica de um poço pode ser feita a partir do cálculo de parâmetros elásticos da formação utilizando a densidade do meio e as velocidades de propagação das ondas compressional e cisalhante na formação rochosa, os quais podem ser obtidos de perfis geofísicos do poço. Em formações sedimentares pouco consolidadas as ferramentas de perfilagem sônica convencionais (monopolares) não conseguem registrar com acuidade a velocidade da onda cisalhante pois a primeira chegada dessa onda é camuflada pela chegada de outras ondas que podem ser mais rápidas que a onda cisalhante num poço perfurado neste tipo de formação. Medidas das velocidades sônicas são feitas em laboratório em amostras da formação, sob condições semelhantes às condições in situ, servindo como ajuste das velocidades registradas no poço pela ferramenta de perfilagem sônica. Para a análise de estabilidade da formação, perfis auxiliares são necessários como o perfil de porosidade, saturação de fluidos e perfis de composição mineralógica da formação rochosa. Exige-se ainda dados de testes de avaliação da formação e de condições do reservatório, mas que são comuns em poços de petróleo, como o teste de formação e os testes de pressurização do poço, tais como o teste de micro-fraturamento hidráulico ou o teste de absorção. A avaliação das tensões principais efetivas que atuam distante do poço, e que não são afetadas pela sua presença, é feita através da associação de um modelo de deformação elástica apropriado e o resultado do teste de pressurização disponível para o poço em estudo. Utilizando resultados clássicos da teoria da elasticidade geral pode-se calcular o campo de tensões modificado na vizinhança da parede do poço devido ao efeito da própria presença do poço ali perfurado e da diferença de pressão existente entre o interior do poço e a formação rochosa. A determinação das propriedades mecânicas da formação a partir das velocidades sônicas e a avaliação do campo de tensões assumindo um modelo elástico de deformação, supõem o meio rochoso no qual as ondas se propagam como elástico, homogêneo e isotrópico. Esta suposição representa a principal aproximação assumida pela metodologia descrita neste trabalho. De posse das propriedades mecânicas da formação e do campo de tensões que age na vizinhança do poço resta definir o critério segundo o qual a rocha sofre instabilidade mecânica quando submetida aquele campo de tensões. Isto permite determinar se, nas condições avaliadas do poço e da formação, haverá quebra da parede do poço por excesso de tensão e, se houver, qual a sua extensão. Assim o problema é como analisar o comportamento mecânico de um poço em uma formação pouco consolidada a partir de perfis geofísicos os quais podem ter problemas no registro das propriedades físicas do meio em formações deste tipo. A metodologia proposta é aplicada a dois intervalos de profundidade pertencentes a dois poços onde arenitos e folhelhos se intercalam e nos quais todos os dados necessários estão disponíveis. Os resultados obtidos mostram que, exceto quando outros mecanismos de quebra da parede do poço agem na formação, a metodologia proposta consegue com sucesso detectar zonas de ocorrência de instabilidade mecânica do poço provocadas por um campo de tensões que excede a resistência mecânica da formação.

In vitro biomechanical comparison of six different fixation methods following 5-mm sagittal split advancement osteotomies

The sagittal split ramus osteotomy (SSRO) is a surgical technique used widely to treat many congenital and acquired mandibular discrepancies. Stabilization of the osteotomy site and the potential for skeletal relapse after the procedure are still major problems. The aim of this study was to compare the mechanical stability of six methods of rigid fixation in SSRO using a biomechanical test model. Sixty polyurethane replicas of human hemimandibles were divided into six groups. In group I, the osteotomies were fixed with two four-hole titanium miniplates; in group II, with one four-hole miniplate; in group III, with one four-hole miniplate + a bicortical screw; in group IV, with a grid miniplate; in group V, with a four-hole locking miniplate; and in group VI, with a six-hole miniplate. A linear load in the premolar region was applied to the hemimandibles. The resistance forces (N) needed to displace the distal segment by 1, 3, and 5 mm were recorded and the data transmitted from the load cell to a computer. One-way analysis of variance with Tukey's post hoc test was performed to compare the means between groups. For the three displacement conditions, there was a strong tendency for the 2.0-mm plate + screw and the grid plate to have higher values.

Streptococcus mutans-derived extracellular matrix in cariogenic oral biofilms

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

Clinical study on survival rate of short implants placed in the posterior mandibular region: resonance frequency analysis

Short implants are increasingly used, but there is doubt about their performance being similar to that of regular implants. The aim of this study was to compare the mechanical stability of short implants vs. regular implants placed in the edentulous posterior mandible. Twenty-three patients received a total of 48 short implants (5 × 5.5 mm and 5 × 7 mm) and 42 regular implants (4 × 10 mm and 4 × 11.5 mm) in the posterior mandible. Patients who received short implants had <10 mm of bone height measured from the bone crest to the outer wall of the mandibular canal. Resonance frequency analysis (RFA) was performed at time intervals T0 (immediately after implant placement), T1 (after 15 days), T2 (after 30 days), T3 (after 60 days), and T4 (after 90 days). The survival rate after 90 days was 87.5% for the short implants and 100% for regular implants (P < 0.05). There was no significant difference between the implants in time intervals T1, T2, T3, and T4. In T0, the RFA values of 5 × 5.5 implants were higher than values of 5 × 7 and 4 × 11.5 implants (P < 0.05). A total of six short implants that were placed in four patients were lost (three of 5 × 5.5 mm and three of 5 × 7 mm). Three lost implants started with high ISQ values, which progressively decreased. The other three lost implants started with a slightly lower ISQ value, which rose and then began to fall. Survival rate of short implants after 90 days was lower than that of regular implants. However, short implants may be considered a reasonable alternative for rehabilitation of severely resorbed mandibles with reduced height, to avoid performing bone reconstruction before implant placement. Patients need to be aware of the reduced survival rate compared with regular implants before implant placement to avoid disappointments.

Projeto estrutural de galpão metálico segundo recomendações da NBR8800

This work deals in a general way, the history and advantages of steel buildings, as well as its increasing usage in Brazil in the last century. This work also generally describes some types and its uses of metal frame. It also demonstrates the use of the NBR 8800: 2008 standard and its calculation methods through the scale out materials regulated in Brazil for an industrial warehouse project small and simple portico metal frame. Given that the construction requirements include a locational influence following the normative indications of the NBR 6123, for the winding scale out, since this effect combined with the permanent loads must be seriously evaluated due to the shape type effort about acting simultaneous axial force and bending moments obeying the limitations applied to the structure according to NBR 8800. As it has been explained the calculations that ensures mechanical stability and suggesting an analysis of the efficiency of the used materials

Projeto estrutural de galpão metálico segundo recomendações da NBR8800

This work deals in a general way, the history and advantages of steel buildings, as well as its increasing usage in Brazil in the last century. This work also generally describes some types and its uses of metal frame. It also demonstrates the use of the NBR 8800: 2008 standard and its calculation methods through the scale out materials regulated in Brazil for an industrial warehouse project small and simple portico metal frame. Given that the construction requirements include a locational influence following the normative indications of the NBR 6123, for the winding scale out, since this effect combined with the permanent loads must be seriously evaluated due to the shape type effort about acting simultaneous axial force and bending moments obeying the limitations applied to the structure according to NBR 8800. As it has been explained the calculations that ensures mechanical stability and suggesting an analysis of the efficiency of the used materials

Identificazione delle Lamine di tipo A come nuovi substrati della protein chinasi Akt/PKB

Akt (also called PKB) is a 63 kDa serine/threonine kinase involved in promotion of cell survival, proliferation a nd metabolic responses downstream the phosphoinositide-3-kinase (PI 3-kinase) signaling pathway. In resting cells, Akt is a predominantly cytosolic enzyme; however generation of PI 3-kinase lipid products recruits Akt to the plasma membrane, resulting in a conformational change which confers full enzymatic activity through the phosphorylation of the membrane-bound protein at two residues, Thr308, and Ser473. Activated Akt redistributes to cytoplasm and nucleus, where phosphorylation of specific substrates occurs. Both the presence and the activity of Akt in the nucleus have been described. An interesting mechanism that mediates nuclear translocation of Akt has been described in human mature T-cell leukemia: the product of TCL1 gene, Tcl1, interacts with the PH domain of phosphorylated Akt, thus driving Akt to the nucleus. In this context, Tcl1 may act as a direct transporter of Akt or may contribute to the formation of a complex that promotes the transport of active Akt to the nucleus, where it can phosphorylate nuclear substrates. A well described nuclear substrate if Foxo. IGF-1 triggers phosphorylation of Foxo by Akt inside the nucleus, where phospho-Foxo associates to 14.3.3 proteins that, in turn, promote its export to the cytoplasm where it is sequestered. Remarkably, Foxo phosphorylation by Akt has been shown to be a crucial event in Akt-dependent myogenesis. However, most Akt nuclear substrates have so far remained elusive, as well as nuclear Akt functions. This lack of information prompted us to undertake a search of substrates of Akt in the nucleus, by the combined use of 2D-separation/mass spectrometry and anti-Akt-phosphosubstrate antibody. This study presents evidence of A-type lamins as novel nuclear substrates of Akt. Lamins are type V intermediate filaments proteins found in the nucleus of higher eukaryotes where, together with lamin-binding proteins, they form the lamina at the nuclear envelope, providing mechanical stability for the nuclear membrane. By coimmunoprecipitation, it is demonstrated here that endogenous lamin A and Akt interact, and that A-type lamins are phosphorylated by Akt both in vitro and in vivo. Moreover, by phosphoaminoacid analysis and mutagenesis, it is further demonstrated that Akt phosphorylates lamin A at Ser404, and, more importantly, that while lamin A/C phosphorylation is stable throughout the cell cycle, phosphorylation of the precursor prelamin A becomes detectable as cells enter the G2 phase, picking at G2/M. This study also shows that lamin phosphorylation by Akt creates a binding site for 14.3.3 adaptors which, in turn, promote prelamin A degradation. While this mechanism is in agreement with a general role of Akt in the regulation of a subset of its substrates, opposite to what has been described, degradation is not mediated through a ubiquitination and proteasomal mechanism but through a lysosomal pathway, as indicated by the reverting action of the lysosomal inhibitor cloroquine. Phosphorylation is a key event in the mitotic breakdown of the nuclear lamina. However, the kinases and the precise sites of phosphorylation are scarcely known. Therefore, these results represent an important breakthrough in this very significant but understudied area. The phosphorylation of the precursor protein prelamin A and its subsequent degradation at G2/M, when both the nuclear envelop and the nuclear lamina disassemble, can be view as part of a mechanism to dispose off the precursor that is not needed in this precise context. The recently reported finding that patients affected by Emery-Dreifuss muscular dystrophy carry a mutation at Arg 401, in the Akt phosphorylation motif, open new perspective that warrant further investigation in this very important field.

Die Funktion von Dystroglycan in der Entwicklung des zentralen Nervensystems

Die Funktion von Dystroglycan in der Entwicklung des zentralen Nervensystems Der DAG ist ein oligomerer Proteinkomplex, der in den Muskelfasern die extrazelluläre Matrix mit dem Zytoskelett verbindet und dadurch der Muskulatur die mechanische Stabilität bei der Kontraktion verleiht. Mutationen des DAG sind die genetische Grundlage für verschiedene Formen von muskulären Dystrophien. Muskuläre Dystrophien sind Krankheiten, die neben einer Degeneration der Muskulatur auch verschiedene ZNS-Defekte aufweisen. Die Funktion des DAG im ZNS ist bisher unbekannt. Um seine Funktion im ZNS zu analysieren, wurde Huhn-Dystroglycan, eine zentrale Komponente des DAG, kloniert. Dystroglycan besteht aus dem extrazellulären Matrixprotein alpha-Dystroglycan und dem transmembranen beta-Dystroglycan. Beide Proteine werden vom selben Gen codiert und posttranslational gespalten. Die Huhn-Dystroglycan-Sequenz ist sehr homolog zu anderen Spezies. Antikörper hergestellt gegen die Interaktionsdomänen von alpha- und beta-Dystroglycan, wurden verwendet um die Interaktion von Dystroglycan selektiv an der Grenzfläche zwischen Gliazellendfüßen und Basallamina in der Retina zu stören. Die Antikörper wurden in vivo intravitreal in Augen von Hühnerembryoanen der Stadien E6 bis E10 injiziert. Die Injektion der Antikörper und entsprechender Fab-Fragmente führten zu schweren Veränderungen in der Retina, unter anderem Hyperproliferation, Auflösung der radialen Struktur der neuroepithelialen Zellen und einer veränderten Schichtung. Diese Ergebnisse deuten darauf hin, daß der DAG am Kontakt der radiären Glizellen zur Basalmembran beteiligt sind.

Maßgeschneiderte Kieselgelträger für die metallocen-katalysierte Polyolefinsynthese

Die vorliegende Arbeit beschäftigt sich mit der Synthese und Charakterisierung von porösen Kieselgelen und ihrem Einsatz als Träger in der heterogenen metallocen-katalysierten Polymerisation von Ethylen. Im Vordergrund stand die Optimierung dieses Prozesses durch das Maßscheidern der Trägereigenschaften unter sonst identischen Polymerisationsbedingungen und das Erforschen des heterogenen Polymerisationsprozesses. Das verwendete Katalysatorsystem (Methylaluminoxan mit Dicyclopentadienylzirkoniumdichlorid) besitzt sehr hohe Aktivitäten und verbleibt im Falle der heterogenen Reaktionsführung im Produkt. Der Mechanismus verläuft über mehrere Phasen, wobei besonderes Augenmerk auf die Trägerpartikelfragmentierung gelenkt wurde. Es wurden zwei Synthesekonzepte für die Herstellung der Träger verfolgt. Im ersten Teil der Arbeit wurden monodisperse unporöse Kieselgel-Nanopartikel (Monosphere) zu Agglomeratträgern über einen Sprühtrocknungsprozess aufgebaut. Die Stabilität der Agglomerate wurde über den Zusatz von monodispersen Kieselgel-Binderpartikeln während der Herstellung variiert. Es wurden sowohl die porenstrukturellen als auch morphologischen Eigenschaften der Agglomeratprodukte untersucht und mit den physiko-chemischen Eigenschaften der Nanopartikel korreliert. In einem zweiten Ansatz wurden sphärische hochporöse Kieselgele mit abgestufter Porosität bei konstanter spezifischer Oberfläche hergestellt und als Träger in der Polyethylensynthese getestet.

Wasserfreie, polymere Protonenleiter für Brennstoffzellen durch Immobilisierung von Imidazol

Es werden neuartige, polymere Protonenleiter vorgestellt die nach dem 'Konzept des polymergebunden Protonensolvens' realisiert wurden. Sie zeigen protonische Leitfähigkeit als intrinsische Eigenschaft, sodass keine zweite, flüssige Phase zur Protonenleitung nötig ist. Verwirklicht wurde das Konzept anhand von kammartigen Siloxanoligomeren und -polymeren, wobei Imidazol als Protonensolvens durch flexible Spacer kovalent an das Rückgrat gebunden ist. Durch Pfropfung mit imidazoltragenden Spacereinheiten wurden ferner Kieselgelnanopartikel oberflächenmodifiziert. Um die Auswirkungen der Immobilisierung von Imidazol auf die Leitfähigkeit zu untersuchen, wurden neben unterschiedlichen Molekulargewichten, die Verbindungen auch jeweils mit verschiedenen Spacerlängen synthetisiert. Die Materialien wurden umfassend charakterisiert und auf ihr thermisches Verhalten, Stabilität, Leitfähigkeit, Diffusion und dielektrisches Verhalten sowie auch nach Dotierung mit Säure untersucht. Thermisch stabil sind die Materialien bis ca. 200°C. Die Leitfähigkeiten betragen bis zu 1,5E-3 S/cm bei 160°C, welche aufgrund der Immobilisierung des Imidazols ausschließlich auf Strukturdiffusion zurückzuführen sind. Die Strukturdiffusion ist vergleichbar mit dem Grotthus-Mechanismus in Wasser und wird durch die lokale Mobilität der Imidazolmoleküle, d.h. durch die Glasübergangstemperatur des Systems bestimmt. Entsprechend wird das für Glasbildner typische Vogel-Tamman-Fulcher-Verhalten für alle untersuchten Transportprozesse gefunden. Die mit abnehmender Glasübergangstemperatur abnehmende mechanische Stabilität der Materialien kann, wie gezeigt ist, durch Compoundierung mit Kieselgelnanopartikeln entscheidend verbessert werden, was eine kostengünstige und aussichtsreiche Möglichkeit zur Herstellung von Membranen für Brennstoffzellen darstellt.

Cellulose based Lithium ion polymer electrolytes for Lithium batteries

The separator membrane in batteries and fuel cells is of crucial importance for the function of these devices. In lithium ion batteries the separator membrane as well as the polymer matrix of the electrodes consists of polymer electrolytes which are lithium ion conductors. To overcome the disadvantage of currently used polymer electrolytes which are highly swollen with liquids and thus mechanically and electrochemically unstable, the goal of this work is a new generation of solid polymer electrolytes with a rigid backbone and a soft side chain structure. Moreover the novel material should be based on cheap substrates and its synthesis should not be complicated aiming at low overall costs. The new materials are based on hydroxypropylcellulose and oligoethyleneoxide derivatives as starting materials. The grafting of the oligoethyleneoxide side chains onto the cellulose was carried out following two synthetic methods. One is based on a bromide derivative and another based on p-toluolsulfonyl as a leaving group. The side chain reagents were prepared form tri(ethylene glycol) monoethyl ether. In order to improve the mechanical properties the materials were crosslinked. Two different conceptions have been engaged based on either urethane chemistry or photosensitive dimethyl-maleinimide derivatives. PEO - graft - cellulose derivatives with a high degree of substitution between 2,9 and 3,0 were blended with lithium trifluoromethane-sulfonate, lithium bis(trifluorosulfone)imide and lithium tetrafluoroborate. The molar ratios were in the range from 0,02 to 0,2 [Li]/[O]. The products have been characterized with nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and laserlight scattering (LS) with respect to their degree of substitution and molecular weight. The effect of salt concentration on ionic conductivity, thermal behaviour and morphology has been investiga-ted with impedance spectroscopy, differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The crosslinking reactions were controlled with dynamic mechanical analysis (DMS). The degree of substitution of our products is varying between 2,8 and 3,0 as determined by NMR. PEO - graft - cellulose derivatives are highly viscous liquids at room temperature with glass transition temperatures around 215 K. The glass transition temperature for the Lithium salt complexes of PEO - graft - cellulose deri-vatives increase with increasing salt content. The maximum conductivity at room temperature is about 10-4 and at 100°C around 10-3 Scm-1. The presence of lithium salt decreases the thermal stability of the complexes in comparison to pure PEO - graft - cellulose derivatives. Complexes heated over 140 – 150°C completely lose their ionic conductivity. The temperature dependence of the conductivity presented as Arrhenius-type plots for all samples is similar in shape and follows a VTF behaviour. This proofs that the ionic transport is closely related to the segmental motions of the polymer chains. Novel cellulose derivatives with grafted oligoethylen-oxide side chains with well-defined chemical structure and high side chain grafting density have been synthesized. Cellulose was chosen as stiff, rod like macromolecule for the backbone while oligoethylen-oxides are chosen as flexible side chains. A maximum grafting density of 3.0 have been obtained. The best conductivity reaches 10-3 Scm-1 at 100°C for a Li-triflate salt complex with a [Li]/[O] ratio of 0.8. The cross-linked complexes containing the lithium salts form elastomeric films with convenient mechanical stability. Our method of cellulose modification is based on relatively cheap and commercially available substrates and as such appears to be a promising alternative for industrial applications.