Experimental and theoretical study of the infrared spectra of BrHI- and BrDI-

Gas phase vibrational spectra of BrHI- and BrDI- have been measured from 6 to 17 mum (590-1666 cm-1) using tunable infrared radiation from the free electron laser for infrared experiments in order to characterize the strong hydrogen bond in these species. BrHI-.Ar and BrDI-.Ar complexes were produced and mass selected, and the depletion of their signal due to vibrational predissociation was monitored as a function of photon energy. Additionally, BrHI- and BrDI- were dissociated into HBr (DBr) and I- via resonant infrared multiphoton dissociation. The spectra show numerous transitions, which had not been observed by previous matrix studies. New ab initio calculations of the potential-energy surface and the dipole moment are presented and are used in variational ro-vibrational calculations to assign the spectral features. These calculations highlight the importance of basis set in the simulation of heavy atoms such as iodine. Further, they demonstrate extensive mode mixing between the bend and the H-atom stretch modes in BrHI- and BrDI- due to Fermi resonances. These interactions result in major deviations from simple harmonic estimates of the vibrational energies. As a result of this new analysis, previous matrix-isolation spectra assignments are reevaluated. (C) 2004 American Institute of Physics.

Rate-dependent fracture toughness of polycrystalline ice

A series of three-point bend tests using single edge notched testpieces of pure polycrystalline ice have been performed at three different temperatures (–20°C, –30°C and –40°C). The displacement rate was varied from 1 mm/min to 100 mm/min, producing the crack tip strain rates from about 10–3 to 10–1 s–1. The results show that (a) the fracture toughness of pure polycrystalline ice given by the critical stress intensity factor (K IC) is much lower than that measured from the J—integral under identical conditions; (b) from the determination of K IC, the fracture toughness of pure polycrystalline ice decreases with increasing strain rate and there is good power law relationship between them; (c) from the measurement of the J—integral, a different tendency was appeared: when the crack tip strain rate exceeds a critical value of 6 × 10–3 s–1, the fracture toughness is almost constant but when the crack tip strain rate is less than this value, the fracture toughness increases with decreasing crack tip strain rate. Re-examination of the mechanisms of rate-dependent fracture toughness of pure polycrystalline ice shows that the effect of strain rate is related not only to the blunting of crack tips due to plasticity, creep and stress relaxation but also to the nucleation and growth of microcracks in the specimen.

Amyloid-like fibrillogenesis through supramolecular helix-mediated self-assembly of tetrapeptides containing non-coded alpha-aminoisobutyric acid (Aib) and 3-aminobenzoic acid (m-ABA)

Single-crystal X-ray diffraction studies of two terminally protected tetrapeptides Boc-Ile-Aib-Val-m-ABA-OMe (I) and Boc-Ile-Aib-Phe-m-ABA-OMe (II) (Aib = alpha-aminoisobutyric acid; m-ABA = meta-aminobenzoic acid) reveal that they form continuous H-bonded helices through the association of double-bend (type III and I) building blocks. NMR Studies support the existence of the double-bend (type Ill and I) structures of the peptides in solution also. Field emission scanning electron-microscopic (FE-SEM) and high-resolution transmission electron-microscopic (HR-TEM) images of the peptides exhibit amyloid-like fibrils in the solid state. The Congo red-stained fibrils of peptide I and II, observed between crossed polarizers, show green-gold birefringence, a characteristic of amyloid fibrils.

Fracture and fatigue of natural fiber-reinforced cementitious composites

This paper presents the results of an experimental study of resistance-curve behavior and fatigue crack growth in cementitious matrices reinforced with eco-friendly natural fibers obtained from agricultural by-products. The composites include: blast furnace slag cement reinforced with pulped fibers of sisal, banana and bleached eucalyptus pulp, and ordinary Portland cement composites reinforced with bleached eucalyptus pulp. Fracture resistance (R-curve) and fatigue crack growth behavior were studied using single-edge notched bend specimens. The observed stable crack growth behavior was then related to crack/microstructure interactions that were elucidated via scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Fracture mechanics models were used to quantify the observed crack-tip shielding due to crack-bridging. The implications of the results are also discussed for the design of natural fiber-reinforced composite materials for affordable housing. (C) 2009 Elsevier Ltd. All rights reserved.

Catalytic properties of thimet oligopeptidase H600A mutant

Thimet oligopeptidase (EC 3.4.24.15, TOP) is a metallo-oligopeptidase that participates in the intracellular metabolism of peptides. Predictions based on structurally analogous peptidases (Dcp and ACE-2) show that TOP can present a hinge-bend movement during substrate hydrolysis, what brings some residues closer to the substrate. One of these residues that in TOP crystallographic structure are far from the catalytic residues, but, moves toward the substrate considering this possible structural reorganization is His(600). In the present work, the role of His(600) of TOP was investigated by site-directed mutagenesis. TOP H600A mutant was characterized through analysis of S(1) and S(1)`, specificity, pH-activity profile and inhibition by JA-2. Results showed that TOP His(600) residue makes important interactions with the substrate, supporting the prediction that His(600) moves toward the substrate due to a hinge movement similar to the Dcp and ACE-2. Furthermore, the mutation H600A affected both K(m) and k(cat), showing the importance of His(600) for both substrate binding and/or product release from active site. Changes in the pH-profile may indicate also the participation of His(600) in TOP catalysis, transferring a proton to the newly generated NH(2)-terminus or helping Tyr(605) and/or Tyr(612) in the intermediate oxyanion stabilization. (C) 2010 Elsevier Inc. All rights reserved.

Conformational Properties of Angiotensin II and Its Active and Inactive TOAC-Labeled Analogs in the Presence of Micelles. Electron Paramagnetic Resonance, Fluorescence, and Circular Dichroism Studies

The interaction between angiotensin II (AII, DRVYIHPF) and its analogs carrying 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (TOAC) and detergents-negatively charged sodium dodecyl sulfate (SDS) and zwitterionic N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS)-was examined by means of EPR, CD, and fluorescence. EPR spectra of partially active TOAC(1)-AII and inactive TOAC(3)-AII in aqueous solution indicated fast tumbling, the freedom of motion being greater at the N-terminus. Line broadening occurred upon interaction with micelles. Below SDS critical micelle concentration, broader lines indicated complex formation with tighter molecular packing than in micelles. Small changes in hyperfine splittings evinced TOAC location at the micelle-water interface. The interaction with anionic micelles was more effective than with zwitterionic micelles. Peptide-micelle interaction caused fluorescence increase. The TOAC-promoted intramolecular fluorescence quenching was more, pronounced for TOAC(3)-AII because of the proximity between the nitroxide and Tyr(4). CD spectra showed that although both AII and TOAC(1)-AII presented flexible conformations in water, TOAC(3)-AII displayed conformational restriction because of the TOAC-imposed bend (Schreier et al., Biopolymers 2004, 74, 389). In HPS, conformational changes were observed for the labeled peptides at neutral and basic pH. In SDS, all peptides underwent pH-dependent conformational changes. Although the spectra suggested similar folds for All and TOAC(1)-AII, different conformations were acquired by TOAC(3)-AII. The membrane environment has been hypothesized to shift conformational equilibria so as to stabilize the receptor-bound conformation of ligands. The fact that TOAC(3)-AII is unable to acquire conformations similar to those of native AII and partially active TOAC(1)-AII is probably the explanation for its lack of biological activity. (C) 2009 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 92: 525-537, 2009.

Soda-Treated Sisal/Polypropylene Composites

Treated sisal fibers were used as reinforcement of polypropylene (PP) composites, with maleic anhydride-grafted PP (MAPP) as coupling agent. The composites were made by melting processing of PP with the fiber in a heated roller followed by multiple extrusions in a single-screw extruder. Injection molded specimens were produced for the characterization of the material. In order to improve the adhesion between fiber and matrix and to eliminate odorous substances, sisal fibers were treated with boiling water and with NaOH solutions at 3 and 10 wt.%. The mechanical properties of the composites were assessed by tensile, bend and impact tests. Additionally, the morphology of the composites and the adhesion at he fiber-matrix interface were analyzed by SEM. The fiber treatment led to very light and odorless materials, with yields of 95, 74 and 62 wt.% for treatments with hot water, 3 and 10 wt.% soda solution respectively. Fiber treatment caused an appreciable change in fiber characteristics, yet the mechanical properties under tensile and flexural tests were not influenced by that treatment. Only the impact strength increased in the composites with alkali-treated sisal fibers.

Brytmånens utformning vid trädfällning - Jämförande studier av böjmotstånd och gångjärnseffekt : Designing felling hinge in tree felling - Comparative studies of bending resistance and hinge effect

Vid trädfällning med motorsåg sparar man en så kallad brytmån som skall fungera som ett gång¬järn när trädet fälls. Om brytmånen går av tidigt finns en risk att trädet faller okontrolle¬rat. De rekommendationer som finns säger att brytmånens bredd skall göras proportionell mot trädets diameter. Genom att teoretiskt och praktiskt undersöka vilka krafter brytmånen utsätts för och vad den håller för har det varit möjligt att dra vissa slutsatser om hur en bra brytmån skall se ut. Ett viktigt resultat är att en bred brytmån (över 30-40 mm) är mycket trög att böja och inte fungerar i det avseendet att den går av redan vid små böjningar. Teoretiska be¬räkningar och praktiska försök visar att en relativt smal brytmån håller för belastningen vid rakt motlut även på stora träd. Som ny rekommendationen föreslås att brytmånens bredd inte bör vara mer än 30 mm. Av försöken kan man också dra slutsatsen att frusen ved är stel och brister tidigt, varför svår¬fällda träd inte bör fällas när veden är fryst.A felling hinge is used when felling trees by help of chain saw. If the hinge breaks early in the fall of the tree there is a great risk that the tree will fall without control. Present recommenda¬tions in Sweden say that the thickness of the felling hinge shall be made in proportion to the stem diameter. By use of theoretical and practical examinations of the forces stressing the felling hinge, and the strength of the wood itself, it has been possible to draw conclusions regarding the correct design of a felling hinge. One important result is that a thick felling hinge (over 30-40 mm) is very hard to bend and does not work well as it looses most of its strength already at a small forward bending angel. Theoretical calculations and practical tests show that a relatively narrow felling hinge will manage very well the forces when felling trees with lean opposite to the felling direction even for large trees. Our new recommendation is that the thickness of the felling hinge in normal Swedish conditions should not exceed 30 mm. Through the studies it can also be seen that frozen, brittle wood breaks at small bending angels. For that reason particularly difficult trees not should be felled when the wood is frozen.

Estudo da influência da temperatura de brasagem nas uniões zircônia/aço inox 304 utilizando metalização mecânica

Metal-Ceramic (M/C) Zirconia-stainless steel interfaces have been processed through brazing techniques due to the excellent combination of properties such as high temperature stability, high corrosion resistance and good mechanical properties. However, some M/C interfaces show some defects, like porosity and cracks results in the degradation of the interfaces, leading even to its total rupture. Most of time, those defects are associated with an improper brazing parameters selection to the M/C system. In this work, ZrO2 Y-TZP and ZrO2 Mg - PSZ were joint with the stainless steel grade 304 by brazing using a eutectic silver-copper (Ag28Cu) interlayer alloy with different thermal cycles. Ceramic surfaces were previous mechanically metallized with titanium to improve adhesion of the system. The effect of temperature on the M/C interface was studied. SEM-EDS and 3 point flexural bend test were performed to evaluate morphology, chemical composition and mechanical resistance of the M/C interfaces. Lower thermal cycle temperatures produced better results of mechanical resistance, and more regular/ homogeneous reaction layers between braze alloy and metal-ceramic surfaces. Also was proved the AgCu braze alloy activation in situ by titanium

Filtros acústicos em cristais fonônicos

In this work, we have studied the acoustic phonon wave propagation within the periodic and quasiperiodic superlattices of Fibonacci type. These structures are formed by phononic crystals, whose periodicity allows the raise of regions known as stop bands, which prevent the phonon propagation throughout the structure for specific frequency values. This phenomenon allows the construction of acoustic filters with great technological potential. Our theoretical model were based on the method of the transfer matrix, thery acoustics phonons which describes the propagation of the transverse and longitudinal modes within a unit cell, linking them with the precedent cell in the multilayer structure. The transfer matrix is built taking into account the elastic and electromagnetic boundary conditions in the superllatice interfaces, and it is related to the coupled differential equation solutions (elastic and electromagnetic) that describe each model under consideration. We investigated the piezoelectric properties of GaN and AlN the nitride semiconductors, whose properties are important to applications in the semiconductor device industry. The calculations that characterize the piezoelectric system, depend strongly on the cubic (zinc-bend) and hexagonal (wurtzite) crystal symmetries, that are described the elastic and piezoelectric tensors. The investigation of the liquid Hg (mercury), Ga (gallium) and Ar (argon) systems in static conditions also using the classical theory of elasticity. Together with the Euler s equation of fluid mechanics they one solved to the solid/liquid and the liquid/liquid interfaces to obtain and discuss several interesting physical results. In particular, the acoustical filters obtained from these structures are again presented and their features discussed

Determining the Optimum Processing Parameters of Glass-like Carbon Using Weibull Analysis of its Fracture Behaviour

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

Evidências da herança geotectônica pré-cambriana na geração da barcia potiguar: um estudo geofísico multdisciplinar

The 3D gravity modeling of the Potiguar rift basin consisted of a digital processing of gravity and aeromagnetic data, subsidized by the results of Euler deconvolution of gravity and magnetic data and the interpretation of seismic lines and wells descriptions. The gravity database is a compilation of independent geophysical surveys conducted by several universities, research institutions and governmental agencies. The aeromagnetic data are from the Bacia Potiguar and Plataforma Continental do Nordeste projects, obtained from the Brazilian Petroleum Agency (ANP). The solutions of the Euler Deconvolution allowed the analysis of the behavior of the rift main limits. While the integrated interpretation of seismic lines provided the delimitating horizons of the sedimentary formations and the basement top. The integration of these data allowed a 3D gravity modeling of basement topography, allowing the identification of a series of internal structures of the Potiguar rift, as well intra-basement structures without the gravity effect of the rift. The proposed inversion procedure of the gravity data allowed to identify the main structural features of the Potiguar rift, elongated in the NE-SW direction, and its southern and eastern faulted edges, where the sedimentary infill reachs thicknesses up to 5500 m. The southern boundary is marked by the Apodi and Baixa Grande faults. These faults seem to be a single NW-SE oriented fault with a strong bend to NE-SW direction. In addition, the eastern boundary of the rift is conditioned by the NE-SW trending Carnaubais fault system. It was also observed NW-SE oriented faults, which acted as transfer faults to the extensional efforts during the basin formation. In the central part of the residual anomaly map without the gravity effect of the rift stands out a NW-SE trending gravity high, corresponding to the Orós-Jaguaribe belt lithotypes. We also observe a gravity maximum parallel to the Carnaubais fault system. This anomaly is aligned to the eastern limit of the rift and reflects the contact of different crustal blocks, limited by the eastern ward counterpart of the Portalegre Shear Zone

Changes in the stiffness of demineralized dentin following application of tooth whitening agents

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

Current status of pulp capping with dentin adhesive systems: a review

Several studies have assessed the morphology and thickness of hybrid layer, the dentin bend strengths as well as sealing ability of dentin adhesive systems. However, few in vivo studies have evaluated the biocompatibility of the adhesive systems following application to deep dentin or directly to the pulp of human teeth. Many studies performed in non-human primate teeth or teeth of rats have reported pulp healing and dentin bridging following pulp capping with bonding agents. In addition, a few clinical and radiographical reports of the success of resin pulp capping have been described in the dental literature.Objectives: the aim of this review was to evaluate the literature on pulp responses following total acid etching and application of adhesive resins on deep cavities or pulp exposures. In addition, the clinical/radiographical evidence for the apparent success of vital pulp therapy and results obtained from animal and human studies were compared and discussed.Significance and conclusions: the self-etching adhesive systems may be useful and safe when applied on dentin, In contrast, persistent inflammatory reactions as well as delay in pulpal healing and failure of dentin bridging were seen in human pulps capped with bonding agents. The results observed in animal teeth cannot be directly extrapolated to human clinical conditions. Consequently, vital pulp therapy using acidic agents and adhesive resins seems to be contraindicated. (C) 2000 Academy of Dental Materials. Published by Elsevier B.V. Ltd. All rights reserved.

Effect of microwave disinfection on the flexural strength of hard chairside reline resins

Objectives: This study investigated the effect of microwave disinfection (650 W/6 min) on the flexural strength of five hard chairside reline resins (Kooliner, Duraliner II, Tokuso Rebase Fast, Ufi Get Hard, New Truliner) and one denture base resin (Lucitone 550).Methods: Thirty-two specimens (3.1x10x64 mm) from each acrylic resin were produced and divided into four groups of eight specimens each. The flexural test was performed after polymerization (G1), after two cycles of microwave disinfection (G2), after 7 days storage in water at 37 degrees C (G3) and after seven cycles of microwave disinfection (G4). Specimens from group G4 were microwaved daily being stored in water at 37 degrees C between exposures. The specimens were placed in three-point bend fixture in a MTS machine and loaded until failure. The flexural values (MPa) were submitted to ANOVA and Tukey's test (p=0.05).Results: Two cycles of microwave disinfection promoted a significant increase in flexural strength for materials Kooliner and Lucitone 550. After seven cycles of microwave disinfection, materials Kooliner and New Truliner showed a significant increase (p<0.05) in flexural values. The flexural strength of the material Tokuso Rebase was not significantly affected by microwave irradiation. Seven cycles of microwave disinfection resulted in a significant decrease in the flexural strength of material Duraliner II. Material Ufi Get Hard was the only resin detrimentally affected by microwave disinfection after two and seven cycles.Conclusions: Microwave disinfection did not adversely affect the flexural strength of all tested materials with the exception of material Ufi Get Hard. (c) 2005 Elsevier Ltd. All rights reserved.