Composite Thin Film Obtained Using Tetraethoxysilane and Aimed at VOCs Detection

The aim of this work was production of tetraethoxysilane (TEOS) plasma polymerized thin films and optimization of their physical-chemical characteristic for sensor development. The films were analyzed using several techniques. It was possible to produce composites (graphite clusters imbibed by silicon oxide film) made from only one reactant (TEOS). Deposition rate can vary significantly, reaching a maximum of 30 nm/min; cluster formation and their size widely depending on deposition parameters. The film surface was hydrophobic but can be wetted by organic compounds, probably due to carbon radicals. These films are good candidates for sensor development.

Estudo comparativo de filmes de corantes fenotiazínicos na superfície de eletrodo de carbono vítreo e adsorvidos em titânio fosfatado e suas aplicações eletroanalíticas

Pós-graduação em Ciência dos Materiais - FEIS

Electroanalytical detection of pindolol: comparison of unmodified and reduced graphene oxide modified screen-printed graphite electrodes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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)

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).

Electrochemical detection of carbamate pesticides in fruit and vegetables with a biosensor based on acetylcholinesterase immobilised on a composite of polyaniline-carbon nanotubes

A sensitive electrochemical acetylcholinesterase (AChE) biosensor was successfully developed on polyaniline (PANI) and multi-walled carbon nanotubes (MWCNTs) core-shell modified glassy carbon electrode (GC), and used to detect carbamate pesticides in fruit and vegetables (apple, broccoli and cabbage). The pesticide biosensors were applied in the detection of carbaryl and methomyl pesticides in food samples using chronoamperometry (CA). The GC/MWCNT/PANI/AChE biosensor exhibited detection limits of 1.4 and 0.95 mu mol L-1, respectively, for carbaryl and methomyl. These detection limits were below the allowable concentrations set by Brazilian regulation standards for the samples in which these pesticides were analysed. Reproducibility and repeatability values of 2.6% and 3.2%, respectively, were obtained in the conventional procedure. The proposed biosensor was successfully applied in the determination of carbamate pesticides in cabbage, broccoli and apple samples without any spiking procedure. The obtained results were in full agreement with those from the HPLC procedure. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis and characterization of CeO2-graphene composite

The synthesis and characterization of graphite oxide (GO), graphene (GS), and the composites: GS-CeO2 and GO-CeO2 are reported. This synthesis was carried out by mixing aqueous solutions of CeCl3 center dot 7H(2)O and GO, which yields the oxidized composite GO-CeO2. GO-CeO2 was hydrothermally reduced with ethylene glycol, at 120 A degrees C, yielding the reduced composite GS-CeO2. GO, GS ,and the composites with CeO2 were characterized by CHN, TG/DTG, BET, XRD, SEM microscopy, FTIR, and Raman spectroscopy. The estimation of crystallite size of CeO2 anchored on GO and on GS by Raman, XRD, and SEM agreed very well showing diameters about 5 nm. The role of particles of CeO2 coating carbon sheets of GO and GS was discussed.

Low content cerium oxide nanoparticles on carbon for hydrogen peroxide electrosynthesis

A comparative study using different proportions of CeO2/C (4%, 9% and 13% CeO2) was performed to produce H2O2, a reagent used in the oxidation of organic pollutants and in electro-Fenton reactions for the production of the hydroxyl radical (OH center dot), a strong oxidant agent used in the electrochemical treatment of aqueous wastewater. The CeO2/C materials were prepared by a modified polymeric precursor method (PPM). X-ray diffraction analysis of the CeO2/C prepared by the PPM identified two phases. CeO2 and CeO2. The average size of the crystallites in these materials was close to 7 nm. The kinetics of the oxygen reduction reaction (ORR) were evaluated by the rotating ring-disk electrode technique. The results showed that the 4% CeO2/C prepared by the PPM was the best composite for the production of H2O2 in a 1 mol L-1 NaOH electrolyte solution. For this material, the number of electrons transferred and the H2O2 percentage efficiency were 3.1 and 44%, respectively. The ring-current of the 4% CeO2/C was higher than that of Vulcan carbon, the reference material for H2O2 production, which produced 41% H2O2 and transferred 3.1 electrons per molecule of oxygen. The overpotential for this reaction on the ceria-based catalyst was substantially lower (approximately 200 mV), demonstrating the higher catalytic performance of this material. Gas diffusion electrodes (GDE) containing the catalyst were used to evaluate the real amount of H2O2 produced during exhaustive electrolysis. The 4% CeO2/C GDE produced 871 mg L-1 of H2O2, whereas the Vulcan carbon GDE produced a maximum amount of only 407 mg L-1. Thus, the 4% CeO2/C electrocatalyst prepared by the PPM is a promising material for H2O2 electrogeneration in alkaline media. (C) 2011 Elsevier B.V. All rights reserved.

Mechanical restoration and failure analyses of a hydrogel and scaffold composite strategy for annulus fibrosus repair

Unrepaired defects in the annulus fibrosus of intervertebral disks are associated with degeneration and persistent back pain. A clinical need exists for a disk repair strategy that can seal annular defects, be easily delivered during surgical procedures, and restore biomechanics with low risk of herniation. Multiple annulus repair strategies were developed using poly(trimethylene carbonate) scaffolds optimized for cell delivery, polyurethane membranes designed to prevent herniation, and fibrin-genipin adhesive tuned to annulus fibrosus shear properties. This three-part study evaluated repair strategies for biomechanical restoration, herniation risk and failure mode in torsion, bending and compression at physiological and hyper-physiological loads using a bovine injury model. Fibrin-genipin hydrogel restored some torsional stiffness, bending ROM and disk height loss, with negligible herniation risk and failure was observed histologically at the fibrin-genipin mid-substance following rigorous loading. Scaffold-based repairs partially restored biomechanics, but had high herniation risk even when stabilized with sutured membranes and failure was observed histologically at the interface between scaffold and fibrin-genipin adhesive. Fibrin-genipin was the simplest annulus fibrosus repair solution evaluated that involved an easily deliverable adhesive that filled irregularly-shaped annular defects and partially restored disk biomechanics with low herniation risk, suggesting further evaluation for disk repair may be warranted. Statement of significance Lower back pain is the leading cause of global disability and commonly caused by defects and failure of intervertebral disk tissues resulting in herniation and compression of adjacent nerves. Annulus fibrosus repair materials and techniques have not been successful due to the challenging mechanical and chemical microenvironment and the needs to restore biomechanical behaviors and promote healing with negligible herniation risk while being delivered during surgical procedures. This work addressed this challenging biomaterial and clinical problem using novel materials including an adhesive hydrogel, a scaffold capable of cell delivery, and a membrane to prevent herniation. Composite repair strategies were evaluated and optimized in quantitative three-part study that rigorously evaluated disk repair and provided a framework for evaluating alternate repair techniques.

Mode II fracture energy in the adhesive bonding of dissimilar substrates: carbon fibre composite to aluminium joints

The end-notched flexure (ENF) test calculates the value of mode II fracture energy in adhesive bonding between the substrates of same nature. Traditional methods of calculating fracture energy in the ENF test are not suitable in cases where the thickness of the adhesive is non-negligible compared with adherent thicknesses. To address this issue, a specific methodology for calculating mode II fracture energy has been proposed in this paper. To illustrate the applicability of the proposed method, the fracture energy was calculated by the ENF test for adhesive bonds between aluminium and a composite material, which considered two different types of adhesive (epoxy and polyurethane) and various surface treatments. The proposed calculation model provides higher values of fracture energy than those obtained from the simplified models that consider the adhesive thickness to be zero, supporting the conclusion that the calculation of mode II fracture energy for adhesives with non-negligible thickness relative to their adherents should be based on mathematical models, such as the method proposed in this paper, that incorporate the influence of this thickness.

Specific and reversible immobilization of proteins tagged to the affinity polypeptide C-LytA on functionalized graphite electrodes

We have developed a general method for the specific and reversible immobilization of proteins fused to the choline-binding module C-LytA on functionalized graphite electrodes. Graphite electrode surfaces were modified by diazonium chemistry to introduce carboxylic groups that were subsequently used to anchor mixed self-assembled monolayers consisting of N,N-diethylethylenediamine groups, acting as choline analogs, and ethanolamine groups as spacers. The ability of the prepared electrodes to specifically bind C-LytA-tagged recombinant proteins was tested with a C-LytA-β-galactosidase fusion protein. The binding, activity and stability of the immobilized protein was evaluated by electrochemically monitoring the formation of an electroactive product in the enzymatic hydrolysis of the synthetic substrate 4-aminophenyl β-D-galactopyranoside. The hybrid protein was immobilized in an specific and reversible way, while retaining the catalytic activity. Moreover, these functionalized electrodes were shown to be highly stable and reusable. The method developed here can be envisaged as a general, immobilization procedure on the protein biosensor field.

Crystallographic orientation and electrode nature are key factors for electric current generation by Geobacter sulfurreducens

We have investigated the influence of electrode material and crystallographic structure on electron transfer and biofilm formation of Geobacter sulfurreducens. Single-crystal gold - Au(110), Au(111), Au(210) - and platinum - Pt(100), Pt(110), Pt(111), Pt(210) - electrodes were tested and compared to graphite rods. G. sulfurreducens electrochemically interacts with all these materials with different attachment kinetics and final current production, although redox species involved in the electron transfer to the anode are virtually the same in all cases. Initial bacterial colonization was fastest on graphite up to the monolayer level, whereas gold electrodes led to higher final current densities. Crystal geometry showed to have an important influence, with Au(210) sustaining a current density of up to 1442 (± 101) μA cm- 2 at the steady state, over Au(111) with 961 (± 94) μA cm- 2 and Au(110) with 944 (± 89) μA cm- 2. On the other hand, the platinum electrodes displayed the lowest performances, including Pt(210). Our results indicate that both crystal geometry and electrode material are key parameters for the efficient interaction of bacteria with the substrate and should be considered for the design of novel materials and microbial devices to optimize energy production.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Segmented polyurethane nanocomposites: Impact of controlled particle size nanofillers on the morphological response to uniaxial deformation

A series of TPU nanocomposites were prepared by incorporating organically modified layered silicates with controlled particle size. To our knowledge, this is the first study into the effects of layered silicate diameter in polymer nanocomposites utilizing the same mineral for each size fraction. The tensile properties of these materials were found to be highly dependent upon the size of the layered silicates. A decrease in disk diameter was associated with a sharp upturn in the stress-strain curve and a pronounced increase in tensile strength. Results from SAXS/SANS experiments showed that the layered silicates did not affect the bulk TPU microphase structure and the morphological response of the host TPU to deformation or promote/hinder strain-induced soft segment crystallization. The improved tensile properties of the nanocomposites containing the smaller nanofillers resulted from the layered silicates aligning in the direction of strain and interacting with the TPU sequences via secondary bonding. This phenomenon contributes predominantly above 400% strain once the microdomain architecture has largely been disassembled. Large tactoids that are unable to align in the strain direction lead to concentrated tensile stresses between the polymer and filler, instead of desirable shear stresses, resulting in void formation and reduced tensile properties. In severe cases, such as that observed for the composite containing the largest silicate, these voids manifest visually as stress whitening.

Electrochemical characteristics of ordered mesoporous carbon used as electrode material in Li-ion battery

Ordered mesoporous carbon CMK-5 was comprehensively tested for the first time as electrode materials in lithium ion battery. The surface morphology, pore structure and crystal structure were investigated by Scanning Electronic Microscopy (SEM), N-2 adsorption technique and X-ray diffraction (XRD) respectively. Electrochemical properties of CMK-5 were studied by galvanostatic cycling and cyclic voltammetry, and compared with conventional anode material graphite. Results showed that the reversible capacity of CMK-5 was 525 mAh/g at the third charge-discharge cycle and that CMK-5 was more compatible for quick charge-discharge cycling because of its special mesoporous structure. Of special interest was that the CMK-5 gave no peak on its positive sweep of the cyclic voltammetry, which was different from all the other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also applied to investigate the charge-discharge characteristics of CMK-5.