Structural and Electrochemical Properties of Lutetium Bis-Octachloro-Phthalocyaninate Nanostructured Films. Application as Voltammetric Sensors

Thin films of the bis[2,3,9,10,16,17,23,24-octachlorophthalocyaninate] lutetium(III) complex (LuPc2Cl32) have been prepared by the Langmuir-Blodgett and the Langmuir-Schaefer (LS) techniques. The influence of the chlorine substituents in the structure of the films and in their spectroscopic, electrochemical and sensing properties has been evaluated. The pi-A isotherms exhibit a monolayer stability greater than the observed in the unsubstituted analogue (LuPc2), being easily transferred to solid substrates, also in contrast to LuPc2. The LB and LS films present a linear growth forming stratified layers, monitored by UV-VIS absorption spectroscopy. The latter also revealed the presence of LuPc2Cl32 in the form of monomers and aggregates in both films. The FTIR data showed that the LuPc2Cl32 molecules present a non-preferential arrangement in both films. Monolayers of LB and LS were deposited onto 6 nm Ag island films to record surface-enhanced resonance Raman scattering (SERRS), leading to enhancement factors close to 2 x 10(3). Finally, LB and LS films deposited onto ITO glass have been successfully used as voltammetric sensors for the detection of catechol. The improved electroactivity of the LB and LS films has been confirmed by the reduction of the overpotential of the oxidation of catechol. The enhancement of the electrocatalytic effect observed in LB and LS films is the result of the nanostructured arrangement of the surface which increases the number of active sites. The sensors show a limit of detection in the range of 10(-5) mol/L.

Design and implementation of wireless sensor networks for impedance-based structural health monitoring using ZigBee and Global System for Mobile Communications

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A virtual experiment for the detection of specific features in the frequency response of a coupled nonlinear and linear oscillator

This paper presents an investigation into some practical issues that may be present in a real experiment, when trying to validate the theoretical frequency response curve of a two degree-of-freedom nonlinear system consisting of coupled linear and nonlinear oscillators. Some specific features, such as detached resonance curves, have been theoretically predicted in multi degree-of-freedom nonlinear oscillators, when subject to harmonic excitation, and the system parameters have been shown to be fundamental in achieving such features. When based on a simplified model, approximate analytical expression for the frequency response curves may be derived, which may be validated by the numerical solutions. In a real experiment, however, the practical achievability of such features was previously shown to be greatly affected by small disturbances induced by gravity and inertia, which led to some solutions becoming unstable which had been predicted to be stable. In this work a practical system configuration is proposed where such effects are reduced so that the previous limitations are overcome. A virtual experiment is carried out where a detailed multi-body model of the oscillator is assembled and the effects on the system response are investigated.

An investigation into the effects of resonances on the time delay estimate for leak detection in buried plastic water distribution pipes

In water distribution systems, old metallic pipes have been replaced by plastic pipes due to their deterioration over time. Although acoustic methods are effective in finding leaks in metallic pipes, they have been found to be problematic when applied to plastic pipes due to the high damping within the pipe wall and the surrounding medium. This is responsible for the leak signal not traveling long distances. Moreover, the leak energy in plastic pipes is generally located at a narrow frequency range located at low frequencies. However, the presence of resonances can narrow even more this frequency range. In order to minimise the influence of background noise and resonances on the calculation of the time delay estimate, band-pass filters are often used to supress undesirable frequency components of the noise. The objective of this paper is to investigate the influence of resonances in the pipe system (pipe, valves, connections and hydrants), on the time delay estimate calculated using acoustic signals. Analytical models and actual leak data collected in a bespoke rig located in the United Kingdom are used to investigate this feature.

Structural characterization of novel chemotactic and mastoparan peptides from the venom of the social wasp Agelaia pallipes pallipes by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Structural and functional evidence for membrane docking and disruption sites on phospholipase A2-like proteins revealed by complexation with the inhibitor suramin

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

Silsesquioxane organofunctionalized with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole: preparation and subsequent reaction with silver and potassium hexacyanoferrate(III) for detection of l-cysteine

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

NUMERICAL AND ANALYTICAL VERIFICATION OF A MULTISCALE COMPUTATIONAL MODEL FOR IMPACT PROBLEMS IN HETEROGENEOUS VISCOELASTIC MATERIALS WITH EVOLVING DAMAGE

Composites are engineered materials that take advantage of the particular properties of each of its two or more constituents. They are designed to be stronger, lighter and to last longer which can lead to the creation of safer protection gear, more fuel efficient transportation methods and more affordable materials, among other examples. This thesis proposes a numerical and analytical verification of an in-house developed multiscale model for predicting the mechanical behavior of composite materials with various configurations subjected to impact loading. This verification is done by comparing the results obtained with analytical and numerical solutions with the results found when using the model. The model takes into account the heterogeneity of the materials that can only be noticed at smaller length scales, based on the fundamental structural properties of each of the composite’s constituents. This model can potentially reduce or eliminate the need of costly and time consuming experiments that are necessary for material characterization since it relies strictly upon the fundamental structural properties of each of the composite’s constituents. The results from simulations using the multiscale model were compared against results from direct simulations using over-killed meshes, which considered all heterogeneities explicitly in the global scale, indicating that the model is an accurate and fast tool to model composites under impact loads. Advisor: David H. Allen

Evaluation of genotoxicity and oxidative damage in painters exposed to low levels of toluene

Toluene is an organic solvent used in numerous processes and products, including industrial paints. Toluene neurotoxicity and reproductive toxicity are well recognized: however, its genotoxicity is still under discussion, and toluene is not classified as a carcinogenic solvent. Using the comet assay and the micronucleus test for detection of possible genotoxic effects of toluene, we monitored industrial painters from Rio Grande do Sul, Brazil. The putative involvement of oxidative stress in genetic damage and the influences of age, smoking, alcohol consumption, and exposure time were also assessed. Although all biomarkers of toluene exposure were below the biological exposure limits, painters presented significantly higher DNA damage (comet assay) than the control group; however, in the micronucleus assay, no significant difference was observed. Painters also showed alterations in hepatic enzymes and albumin levels, as well as oxidative damage, suggesting the involvement of oxidative stress. According to multiple linear regression analysis, blood toluene levels may account for the increased DNA damage in painters. In summary, this study showed that low levels of toluene exposure can cause genetic damage, and this is related to oxidative stress, age, and time of exposure. (C) 2012 Elsevier B.V. All rights reserved.

Early detection of doxorubicin myocardial injury by ultrasonic tissue characterization in an experimental animal model

In the clinical setting, the early detection of myocardial injury induced by doxorubicin (DXR) is still considered a challenge. To assess whether ultrasonic tissue characterization (UTC) can identify early DXR-related myocardial lesions and their correlation with collagen myocardial percentages, we studied 60 rats at basal status and prospectively after 2mg/Kg/week DXR endovenous infusion. Echocardiographic examinations were conducted at baseline and at 8,10,12,14 and 16 mg/Kg DXR cumulative dose. The left ventricle ejection fraction (LVEF), shortening fraction (SF), and the UTC indices: corrected coefficient of integrated backscatter (IBS) (tissue IBS intensity/phantom IBS intensity) (CC-IBS) and the cyclic variation magnitude of this intensity curve (MCV) were measured. The variation of each parameter of study through DXR dose was expressed by the average and standard error at specific DXR dosages and those at baseline. The collagen percent (%) was calculated in six control group animals and 24 DXR group animals. CC-IBS increased (1.29 +/- 0.27 x 1.1 +/- 0.26-basal; p=0.005) and MCV decreased (9.1 +/- 2.8 x 11.02 +/- 2.6-basal; p=0.006) from 8 mg/Kg to 16mg/Kg DXR. LVEF presented only a slight but significant decrease (80.4 +/- 6.9% x 85.3 +/- 6.9%-basal, p=0.005) from 8 mg/Kg to 16 mg/Kg DXR. CC-IBS was 72.2% sensitive and 83.3% specific to detect collagen deposition of 4.24%(AUC=0.76). LVEF was not accurate to detect initial collagen deposition (AUC=0.54). In conclusion: UTC was able to early identify the DXR myocardial lesion when compared to LVEF, showing good accuracy to detect the initial collagen deposition in this experimental animal model.

Molecular detection of enteropathogenic Escherichia coli in asymptomatic captive psittacines

Psittaciformes are one of the most endangered groups of birds, and several Brazilian species are classified between vulnerable and critically endangered. It is thus necessary to identify agents that cause infections in captive wild animals and to assess the risks posed thereof and to design interventions to minimize the possibility of disease outbreaks, leading to the conservation of endangered species. The purpose of this study was to identify enteropathogenic Escherichia coli (EPEC) cloacal isolates from asymptomatic psittacines in captivity and evaluate the distribution of the EPEC pathotype. Cloacal swabs were obtained from 46 asymptomatic birds, and resulting isolates were tested by polymerase chain reaction (PCR) for the presence of the attaching and effacing gene (eae) and bundle-forming pilus structural gene (bfpA) of EPEC. Samples from several species were tested, and three samples were found to be positive for the eae and bfpA genes and characterized as typical EPEC. This is the first report of this pathotype in asymptomatic psittacines. Although certain E. coli strains are more pathogenic than others, various factors should be considered when determining the potential of E. coli isolates to cause disease in captive psittacines. Birds that are positive for the EPEC (typical) strain could be zoonotic sources of infection, and may have acquired these strains through contact with humans or domestic animals. These findings may also be valuable for the long-term management of endangered species ex situ as one EPEC sample was isolated from a Red-tailed Amazon (Amazona brasiliensis).

The beta 2-Adrenoceptor Agonist Formoterol Improves Structural and Functional Regenerative Capacity of Skeletal Muscles From Aged Rat at the Early Stages of Postinjury

Skeletal muscles from old rats fail to completely regenerate following injury. This study investigated whether pharmacological stimulation of beta 2-adrenoceptors in aged muscles following injury could improve their regenerative capacity, focusing on myofiber size recovery. Young and aged rats were treated with a subcutaneous injection of beta 2-adrenergic agonist formoterol (2 mu g/kg/d) up to 10 and 21 days after soleus muscle injury. Formoterol-treated muscles from old rats evaluated at 10 and 21 days postinjury showed reduced inflammation and connective tissue but a similar number of regenerating myofibers of greater caliber when compared with their injured controls. Formoterol minimized the decrease in tetanic force and increased protein synthesis and mammalian target of rapamycin phosphorylation in old muscles at 10 days postinjury. Our results suggest that formoterol improves structural and functional regenerative capacity of regenerating skeletal muscles from aged rats by increasing protein synthesis via mammalian target of rapamycin activation. Furthermore, formoterol may have therapeutic benefits in recovery following muscle damage in senescent individuals.

Use of a Single L1 GPS Receiver for Monitoring Structures: First Results of the Detection of Millimetric Dynamic Oscillations

This paper presents preliminary results to determine small displacements of a global positioning system (GPS) antenna fastened to a structure using only one L1 GPS receiver. Vibrations, periodic or not, are common in large structures, such as bridges, footbridges, tall buildings, and towers under dynamic loads. The behavior in time and frequency leads to structural analysis studies. The hypothesis of this article is that any large structure that presents vibrations in the centimeter-to-millimeter range can be monitored by phase measurements of a single L1 receiver with a high data rate, as long as the direction of the displacement is pointing to a particular satellite. Within this scenario, the carrier phase will be modulated by antenna displacement. During a period of a few dozen seconds, the relative displacement to the satellite, the satellite clock, and the atmospheric phase delays can be assumed as a polynomial time function. The residuals from a polynomial adjustment contain the phase modulation owing to small displacements, random noise, receiver clock short time instabilities, and multipath. The results showed that it is possible to detect displacements of centimeters in the phase data of a single satellite and millimeters in the difference between the phases of two satellites. After applying a periodic nonsinusoidal displacement of 10 m to the antenna, it is clearly recovered in the difference of the residuals. The time domain spectrum obtained by the fast Fourier transform (FFT) exhibited a defined peak of the third harmonic much more than the random noise using the proposed third-degree polynomial model. DOI: 10.1061/(ASCE)SU.1943-5428.0000070. (C) 2012 American Society of Civil Engineers.

Effect of endogenous hydrogen sulfide inhibition on structural and functional renal disturbances induced by gentamicin

Animal models of gentamicin nephrotoxicity present acute tubular necrosis associated with inflammation, which can contribute to intensify the renal damage. Hydrogen sulfide (H2S) is a signaling molecule involved in inflammation. We evaluated the effect of DL-propargylglycine (PAG), an inhibitor of endogenous H2S formation, on the renal damage induced by gentamicin. Male Wistar rats (N = 8) were injected with 40 mg/kg gentamicin (im) twice a day for 9 days, some of them also received PAG (N = 8, 10 mg·kg-1·day-1, ip). Control rats (N = 6) were treated with saline or PAG only (N = 4). Twenty-four-hour urine samples were collected one day after the end of these treatments, blood samples were collected, the animals were sacrificed, and the kidneys were removed for quantification of H2S formation and histological and immunohistochemical studies. Gentamicin-treated rats presented higher sodium and potassium fractional excretion, increased plasma creatinine [4.06 (3.00; 5.87) mg%] and urea levels, a greater number of macrophages/monocytes, and a higher score for tubular interstitial lesions [3.50 (3.00; 4.00)] in the renal cortex. These changes were associated with increased H2S formation in the kidneys from gentamicin-treated rats (230.60 ± 38.62 µg·mg protein-1·h-1) compared to control (21.12 ± 1.63) and PAG (11.44 ± 3.08). Treatment with PAG reduced this increase (171.60 ± 18.34), the disturbances in plasma creatinine levels [2.20 (1.92; 4.60) mg%], macrophage infiltration, and score for tubular interstitial lesions [2.00 (2.00; 3.00)]. However, PAG did not interfere with the increase in fractional sodium excretion provoked by gentamicin. The protective effect of PAG on gentamicin nephrotoxicity was related, at least in part, to decreased H2S formation.

Assessment of cumulative damage by using ultrasonic C-scan on carbon fiber/epoxy composites under thermal cycling

In recent years, structural composites manufactured by carbon fiber/epoxy laminates have been employed in large scale in aircraft industries. These structures require high strength under severe temperature changes of -56° until 80 °C. Regarding this scenario, the aim of this research was to reproduce thermal stress in the laminate plate developed by temperature changes and tracking possible cumulative damages on the laminate using ultrasonic C-scan inspection. The evaluation was based on attenuation signals and the C-scan map of the composite plate. The carbon fiber/epoxy plain weave laminate underwent temperatures of -60° to 80 °C, kept during 10 minutes and repeated for 1000, 2000, 3000 and 4000 times. After 1000 cycles, the specimens were inspected by C-scanning. A few changes in the laminate were observed using the inspection methodology only in specimens cycled 3000 times, or so. According to the found results, the used temperature range did not present enough conditions to cumulative damage in this type of laminate, which is in agreement with the macro - and micromechanical theory.