Molecular and Electronic Structure of the Peptide Subunit of Geobacter sulfurreducens Conductive Phi from First Principles

The respiration of metal oxides by the bacterium Geobacter sulfurreducens requires the assembly of a small peptide (the GS pilin) into conductive filaments termed pili. We gained insights into the contribution of the GS pilin to the pilus conductivity by developing a homology model and performing molecular dynamics simulations of the pilin peptide in vacuo and in solution. The results were consistent with a predominantly helical peptide containing the conserved a-helix region required for pilin assembly but carrying a short carboxy-terminal random-coiled segment rather than the large globular head of other bacterial pilins. The electronic structure of the pain was also explored from first principles and revealed a biphasic charge distribution along the pilin and a low electronic HOMO-LUMO gap, even in a wet environment. The low electronic band gap was the result of strong electrostatic fields generated by the alignment of the peptide bond dipoles in the pilin's alpha-helix and by charges from ions in solution and amino acids in the protein. The electronic structure also revealed some level of orbital delocalization in regions of the pilin containing aromatic amino acids and in spatial regions of high resonance where the HOMO and LUMO states are, which could provide an optimal environment for the hopping of electrons under thermal fluctuations. Hence, the structural and electronic features of the pilin revealed in these studies support the notion of a pilin peptide environment optimized for electron conduction.

Comparison of screening methods for conductive hearing loss identification in children: low-cost proposal

Objective To evaluate the effectiveness of two screening methods (imitanciometry screening and questionnaire) to identify children at risk for conductive hearing loss, comparing this data with complete audiologic evaluation. Methods Of 507 children aged between three and six, 111 completed all procedures. The observational methods used were: imitanciometry screening, a questionnaire to identify risk factors for hearing loss and complete audiologic evaluation. Results obtained in the first two instruments were compared with results from complete audiologic evaluation (gold standard). From these comparisons, sensitivity and specificity, accuracy, positive and negative predictive values, and odds ratio were determined for the two screening methods and for the combination of both methods. Results The two methods applied in series (questionnaire and after imitanciometry screening) showed a greater odds ratio and better correlation between sensitivity and proportion of false-positives (ROC curve). Conclusion Combining the two tests in series improved screening accuracy. This combination was the best tool for identifying children at risk for conductive hearing loss.

Conductive polymer gas sensor for quantitative detection of methanol in Brazilian sugar-cane spirit

A low-cost chemiresistive gas sensor is described, made by the deposition of a thin film of a conductive polymer, poly(2-dodecanoylsulfanyl-p-phenylenevinylene), doped with dodecylbenzenesulfonic acid (10%, w/w), onto interdigitated electrodes. The sensor exhibits linear electrical conductance changes in function of the concentration of methanol present in sugar-cane spirit in the range between 0.05% and 4.0%. Since the sensor is cheap, easy to fabricate, durable, presents low power consumption, and is not sensitive to ethanol, acetic acid or water, it can be used in portable equipments for monitoring methanol levels in distilled alcoholic beverages such as Brazilian sugar-cane spirit (cachaca). (C) 2011 Elsevier Ltd. All rights reserved.

Luminescence properties of the TRIMEB inclusion compound of a europium tris-beta-diketonate

The adduct TRIMEB:Eu(BTA)(3)center dot 2H(2)O was prepared and primarily characterized by photoluminescence (PL), and compared with free Eu(BTA)(3)center dot 2H(2)O. Both spectra show the Eu3+ ion emission, with subtle differences between lines for the free and encapsulated complex. The temperature dependence and chemical stability were studied, taking into account (in the latter case) the PL changes with time. The use of this new material as the emissive layer in OLEDs was tested by its successful incorporation into a device, using a conductive polymer as host. The use of the TRIMEB adduct increased the stability of the device (as compared with the free Eu complex). (C) 2008 Elsevier B.V. All rights reserved.

Use of Gas Diffusion Electrode for the In Situ Generation of Hydrogen Peroxide in an Electrochemical Flow-By Reactor

Hydrogen peroxide is a powerful oxidant that finds application in several areas, but most particularly in the treatment of industrial wastewaters. The aim of the present study was to investigate the effects of applied potential and electrolyte flow conditions on the in situ generation of hydrogen peroxide in an electrochemical flow-by reactor with a gas diffusion electrode (GDE). The electrolyses were performed in an aqueous acidic medium using a GDE constructed with conductive black graphite and polytetrafluoroethylene (80:20 w/w). Under laminar flow conditions (flow rate = 50 L/h), hydrogen peroxide was formed in a maximum yield of 414 mg/L after 2 h at -2.25 V vs Pt //Ag/AgCl (global rate constant = 3.1 mg/(L min); energy consumption = 22.1 kWh/kg). Under turbulent flow (300 L/h), the maximum yield obtained was 294 mg/L after 2 h at -1.75 V vs Pt//Ag/AgCl (global rate constant = 2.5 mg/ (L min); energy consumption = 30.1 kWh/kg).

Geoelectrical mapping of contamination in the cemeteries: the case study in Piracicaba, Sao Paulo/Brazil

This paper presents the results of electrical resistivity methods in the area delineation that was potentially contaminated by liquefaction products, which are also called putrefactive liquids in Vila Rezende municipal cemetery, Piracicaba, So Paulo, Brazil. The results indicate a depth of water table between 3.1 and 5.1 m, with two groundwater direction flows, one to the SW and another to the SE. Due to the contamination plumes, which have the same groundwater direction flow, as well the conductive anomalies observed in the geoelectric sections, the contamination suspicions in the area were confirmed. The probable plume to the SE extends beyond the limits of the cemetery. The location of the conductive anomalies and the probable contamination plumes showed that the contamination is linked with the depth of the water table and the burial time. Mapping using the geostatistical method of ordinary kriging applied to the work drew structural characteristics of the regional phenomenon and spatial behavior of the electrical resistivity data, resulting in continued surfaces. Thus, this method has proved to be an important tool for mapping contamination plumes in cemeteries.

Case study: a 3D resistivity and induced polarization imaging from downstream a waste disposal site in Brazil

A contaminated site from a downstream municipal solid waste disposal site in Brazil was investigated by using a 3D resistivity and induced polarization (IP) imaging technique. This investigation purpose was to detect and delineate contamination plume produced by wastes. The area was selected based on previous geophysical investigations, and chemical analyses carried out in the site, indicating the presence of a contamination plume in the area. Resistivity model has successfully imaged waste presence (rho < 20 Omega m), water table depth, and groundwater flow direction. A conductive anomaly (rho < 20 Omega m) outside wastes placement was interpreted as a contamination plume. Chargeability model was also able to imaging waste presence (m > 31 mV/V), water table depth, and groundwater flow direction. A higher chargeability zone (m > 31 mV/V) outside wastes placement and following conductive anomaly was interpreted as a contamination plume. Normalized chargeability (MN = m/rho) confirmed polarizable zone, which could be an effect of a salinity increase (contamination plume), and the clay presence in the environment.

Preparation and characterization of poly(vinyl butyral)-polyaniline-montmorillonite nanocomposites

Poly(vinyl butyral)-polyaniline-sodium montmorillonite nanocomposites were prepared via polymerization of aniline between clay mineral platelets at two different pH levels (2.0 and 5.0), followed by dispersion of the polyaniline-sodium montmorillonite nanocomposite in a poly(vinyl butyral) solution. A comparison was made of the effect of the pH levels and the polyaniline-sodium montmorillonite nanocomposite precursor on the final structures of the poly(vinyl butyral) nanocomposites and their electrical conductivities. X-ray diffraction patterns revealed the formation of nanocomposites at both pH levels. UV-Vis spectra indicated that the polyaniline formed at both pH levels was conductive, with the UV-Vis spectra presenting a band at 420 nm corresponding to the polaronic form and the beginning of a new band at 600 nm indicating the presence of polaronic segments. FTIR spectra revealed the peaks of the groups present in polyaniline and poly(vinyl butyral) nanocomposites. The electrical conductivities of the polyaniline and poly(vinyl butyral) nanocomposites prepared at pH 2.0 were lower than those of the same nanocomposites prepared at pH 5.0, probably due to the lower formation of polyaniline chains in a more acidic dispersion and to the final configuration of polyaniline in the nanocomposites.

TDEM survey in urban environmental for hydrogeological study at USP campus in Sao Paulo city, Brazil

In this work, some TDEM (Time Domain Electromagnetic) results at USP (University of Sao Paulo) campus in Sao Paulo city, Brazil, are presented. The data were acquired focusing on two mains objectives: (i) to map geoelectrical stratigraphy of Sao Paulo sedimentary basin, emphasizing on hydrogeological studies about sedimentary and crystalline aquifers, and (ii) to analyze the viability of TDEM data acquisition use in urban environment. The study area is located in Sao Paulo basin border, characterized by Resende and Sao Paulo formations, which are constituted by sand-clays sediments over a granite-gneissic basement. Two equipments were used in order to acquire database: Protem47 (low power), and Protem57-MK2 (high power). Capacitive noise affect obtained data with Protem47 due to the presence of metal pipes buried at IAG/USP (Institute of Astronomy, Geophysics, and Atmospheric Science) test site at USP. On the other hand, capacitive noise did not affect acquired data with Protem57-MK2, and the data present high signal to noise ratio. Surveys helped in determining sedimentary and crystalline aquifers, characterized by a fracture zone with water inside basin basement (conductive zone). Results show good agreement with local geology obtained from lithological boreholes located in the study areas. Moreover, it shows that TDEM method can be used in urban environments with a countless potential in hydrogeological studies, offering great reliability. Studies showed that main TDEM-method limitation at USP was the lack of space for opening the transmitter loop. Results are very promising and open new perspectives for TDEM-method use in urban environments as this area remains unexplored. (C) 2011 Elsevier B.V. All rights reserved.

Stabilization of polyaniline by the incorporation of magnetite nanoparticles

Nanocomposites obtained from the polymerization of aniline in the presence of nanoparticles of magnetite (Fe3O4) have been investigated in previous studies. However, there is a lack of information available on the redox interaction of the nanoparticle/conductive polymer couple and the stability that such an oxide can give to the organic phase. In this work, Fe3O4 nanoparticles were incorporated into a PANi matrix by the in-situ oxidative polymerization method. A combination of X-ray diffraction, Mossbauer spectroscopy, transmission electronic microscopy, UV-visible spectroscopy as well as the cyclic voltammetric and Raman spectroscopy techniques, was used to understand the redox effect that the partially oxidized nanoparticles produced on the polymer. It was found that magnetite greatly stabilised PANi, mainly by enhancing the Leucoemeraldine/Emeraldine redox couple and also by reducing the bipolaronic state. (C) 2011 Elsevier B.V. All rights reserved.

Regioregular improvement on the oxidative polymerization of poly-3-octylthiophenes by slow addition of oxidant at low temperature

Many pathways can be used to synthesize polythiophenes derivatives. The polycondensation reactions performed with organometallics are preferred since they lead to regioregular polymers (with high content of heat-to-tail coupling) which have enhanced conductivity and luminescence. However, these pathways have several steps; the reactants are highly moisture sensitive and expensive. On the other hand, the oxidative polymerization using FeCl3 is a one-pot reaction that requires less moisture sensitive reactants with lower cost, although the most common reaction conditions lead to polymers with low regioregularity. Here, we report that by changing the reaction conditions, such as FeCl3 addition rate and reaction temperature, poly-3-octylthiophenes with different the regioregularities can be obtained, reaching about 80% of heat-to-tail coupling. Different molar mass distributions and polydispersivities were obtained. The preliminary results suggest that the oxidative polymerization process could be improved to yield polythiophenes with higher regioregularity degree and narrower molar mass distributions by just setting some reaction conditions. We also verified that it is possible to solvent extract part of the lower regioregular fraction of the polymer further improving the regioregularity degree. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Amplificação por condução óssea em malformações congênitas: benefício e satisfação

Hearing loss is one of the most common clinical findings in subjects with malformations of the ear. Treatment consists of surgery and/or adapt a hearing aid amplification by bone (HA VO). Early intervention is critical to auditory stimulation and development of speech and language. OBJECTIVE: To characterize the audiological profile of subjects with congenital malformation of the external ear and/or middle and evaluate the benefit and satisfaction of using HA VO. METHOD: A descriptive study, subjects with bilateral congenital malformations of the external ear and/or middle, conductive or mixed hearing loss, moderate or severe and HA VO users. Evaluation of the benefit test using sentence recognition in noise and measures of functional gain and satisfaction assessment questionnaire using international IQ - HA. RESULTS: 13 subjects were evaluated, 61% were male and 80% with moderate conductive hearing loss or severe. There was better performance in the evaluation proposal, provided with HA when compared to the condition without HA. CONCLUSION: HA VO showed advantages for the population studied and should be considered as an option for intervention. Satisfaction was confirmed by elevated scores obtained in IQ - HA.

Questionnaire for monitoring auditory and language development in the first year of life

Purpose: To validate a monitoring questionnaire about hearing and language development applied by community health agents in the first year of life. Methods: Seventy six community health agents, previously trained on infant hearing health, administered a questionnaire to the families of 304 children with ages from 0 to 1 year. The questionnaire contains questions regarding hearing and language development and, for all age groups, the question “Does your child hear well?” was presented. The validity of the questionnaire was assessed by analyzing false positive and false negative rates of the identified children. A double-blind study was conducted so that all children assessed by the questionnaire were submitted to hearing evaluation performed by audiologists. Results: Four children (1.32%) were diagnosed with sensorineural hearing loss (two unilateral), and 69 (22.7%) with conductive hearing loss. The monitoring questionnaire showed specificity of 96% and sensitivity of 67%, with a false-negative rate of 33% for not identifying the unilateral hearing loss, and a false-positive rate of 4%. Conclusion: The questionnaire used has shown to be feasible and relevant to actions of the community health agents of the Family Health Strategy program, with high specificity and moderate sensitivity. The use of the validated instrument should be considered to complement Newborn Hearing Screening Programs, in order to identify late onset or acquired hearing loss.

Monitoramento de crianças com indicadores de risco para a deficiência auditiva

Purpose: to describe the proposal of monitoring children in the first year of life, who were not identified in the newborn hearing screening program but had risk factors for hearing loss. Method: the study included 258 risk children who had obtained the result “pass” in the Universal Newborn Hearing Screening Program of Hospital Santa Isabel – Bauru/SP, from June to November 2008. It was applied by the telephone, a validated questionnaire in a previous study, containing questions about hearing and language. For each question there were two possible answers: “yes” or “no” and we considered “failure” to obtain at least one “no” answer. With such result, the child was scheduled to perform an immediate hearing evaluation. Results: the questionnaire was applied with 169 families; with the others, there was no contact. From the total, 164 (97,04%) obtained “passed” and five (2,96%) “failed”. Between these five children, only three showed up for hearing evaluation and one had no disorders; two presented conductive hearing loss. It was observed distinct prevalence among the risk factors and there was no relation (p>0,05) of the risk factors with the evasion in the monitoring process. Conclusion: the monitoring through a questionnaire applied by telephone proved to be feasible, however, it is necessary to develop strategies to support their execution.

Estimation of transpiration of the 'Valencia' orange young plant using thermal dissipation probe method

Most studies on measures of transpiration of plants, especially woody fruit, relies on methods of heat supply in the trunk. This study aimed to calibrate the Thermal Dissipation Probe Method (TDP) to estimate the transpiration, study the effects of natural thermal gradients and determine the relation between outside diameter and area of xylem in 'Valencia' orange young plants. TDP were installed in 40 orange plants of 15 months old, planted in boxes of 500 L, in a greenhouse. It was tested the correction of the natural thermal differences (DTN) for the estimation based on two unheated probes. The area of the conductive section was related to the outside diameter of the stem by means of polynomial regression. The equation for estimation of sap flow was calibrated having as standard lysimeter measures of a representative plant. The angular coefficient of the equation for estimating sap flow was adjusted by minimizing the absolute deviation between the sap flow and daily transpiration measured by lysimeter. Based on these results, it was concluded that the method of TDP, adjusting the original calibration and correction of the DTN, was effective in transpiration assessment.