Characteristics of pyridine adsorption on Au(111) and Au(210) by EIS parameters fitting procedure

Some aspects of the application of electrochemical impedance spectroscopy to studies of solid electrode / solution interface, in the absence of faradaic processes, are analysed. In order to perform this analysis, gold electrodes with (111) and (210) crystallographic orientations in an aqueous solution containing 10 mmol dm-3 KF, as supporting electrolyte, and a pyridine concentration varying from 0.01 to 4.6 mmol dm-3, were used. The experimental data was analysed by using EQUIVCRT software, which utilises non-linear least squares routines, attributing to the solid electrode / solution interface behaviour described by an equivalent circuit with a resistance in series with a constant phase element. The results of this fitting procedure were analysed by the dependence on the electrode potential on two parameters: the pre-exponential factor, Y0, and the exponent n f, related with the phase angle shift. By this analysis it was possible to observe that the pyridine adsorption is strongly affected by the crystallographic orientation of the electrode surface and that the extent of deviation from ideal capacitive behaviour is mainly of interfacial origin.

Compliant Multi-electrode Micro-channel Array for Recording Afferent Nerve Activity

We have fabricated a compliant neural interface to record afferent nerve activity. Stretchable gold electrodes were evaporated on a polydimethylsiloxane (PDMS) substrate and were encapsulated using photo-patternable PDMS. The built-in microstructure of the gold film on PDMS allows the electrodes to twist and flex repeatedly, without loss of electrical conductivity. PDMS microchannels (5mm long, 100μm wide, 100μm deep) were then plasma bonded irreversibly on top of the electrode array to define five parallel-conduit implants. The soft gold microelectrodes have a low impedance of ~200kΩ at the 1kHz frequency range. Teased nerves from the L6 dorsal root of an anaesthetized Sprague Dawley rat were threaded through the microchannels. Acute tripolar recordings of cutaneous activity are demonstrated, from multiple nerve rootlets simultaneously. Confinement of the axons within narrow microchannels allows for reliable recordings of low amplitude afferents. This electrode technology promises exciting applications in neuroprosthetic devices including bladder fullness monitors and peripheral nervous system implants.

Vanadium oxide-porphyrin nanocomposites as gas sensor interfaces for probing low water content in ethanol

Vanadium pentoxide xerogels (VXG) incorporating meso(3- and 4-pyridyl)porphyrin cobalt(III) species coordinated to four [Ru(bipy)(2)Cl](+) complexes were employed as gas sensing materials capable of detecting small amounts of water in commercial ethanol and fuel supplies. According to their X-ray diffraction data, the original VXG lamellar framework was maintained in the nanocomposite material, but the interlamellar distance increased from 11.7 to 15.2 angstrom, reflecting the intercalation of the porphyrin species into the vanadium pentoxide matrix. The films generated by direct deposition of the nanocomposite aqueous suspensions exhibited good electrical and electrochemical performance for application in resistive sensors. The analysis of water in ethanol and fuels was carried out successfully using an especially designed electric setup incorporating a laminar gas flow chamber and interdigitated gold electrodes coated with the nanocomposites. (C) 2010 Elsevier B.V. All rights reserved.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.

Mass transport effects in the borohydride oxidation reaction-Influence of the residence time on the reaction onset and faradaic efficiency

The borohydride oxidation reaction (BOR) was studied on Pt and Au electrodes by cyclic voltammetry in dilute alkaline borohydride solutions (0.1 M NaOH + 10(-3) mol L(-1) NaBH(4)). More specifically, the electrodes were considered as either Vulcan XC72-supported Pt or Au (noted as Pt/C and Au/C, respectively) active layers or smooth Pt or Au surfaces, the latter possibly being covered by a layer of (non-metalized) Vulcan XC72 carbon powder. The BOR onset potential and the number of electrons (n(e-)) exchanged per BH(4)(-) anion (faradaic efficiency) were investigated for these electrodes, to determine whether the residence time of reaction intermediates (at the electrode surface or inside the porous layer) does influence the overall reaction pathway/completion. For the carbon-supported platinum, n(e-) strongly depends on the thickness of the active layer. While thin (ca. 0.5 mu m-thick) Pt/C active layers yield n(e-) < 4, thick layers (approximately 3 mu m) yield n(e-)approximate to 8, which can be ascribed to the sufficient residence time of the molecules formed within the active layer (H(2), by heterogeneous hydrolysis, or BOR intermediates) enabling further (near-complete) oxidation. This puts into evidence that not only the nature of the electrocatalyst is important to reach high BOR efficiency, but also the structure/thickness of the active layer. The same trend applies for Au/C active layers and for smooth Pt or Au surfaces covered with a layer of (inactive) Vulcan XC72. In addition, the BOR onset usually shifts negative when the reaction intermediates are trapped, which suggests that some of the intermediates are more easily oxidized than BH(4)(-) itself; based on literature data, BH(3)OH(-) species is a likely candidate. (C) 2011 Elsevier B.V. All rights reserved.

Comparison of the analytical performance of electrophoresis microchannels fabricated in PDMS, glass, and polyester-toner

This paper compares the analytical performance of microchannels fabricated in PDMS, glass, and polyester-toner for electrophoretic separations. Glass and PDMS chips were fabricated using well-established photolithographic and replica-molding procedures, respectively. PDMS channels were sealed against three different types of materials: native PDMS, plasma-oxidized PDMS, and glass. Polyester-toner chips were micromachined by a direct-printing process using an office laser printer. All microchannels were fabricated with similar dimensions according to the limitations of the direct-printing process (width/depth 150 mu m/12 mu m). LIF was employed for detection to rule out any losses in separation efficiency due to the detector configuration. Two fluorescent dyes, coumarin and fluorescein, were used as model analytes. Devices were evaluated for the following parameters related to electrophoretic separations: EOF, heat dissipation, injection reproducibility, separation efficiency, and adsorption to channel wall.

Exploiting Distinct Molecular Architectures of Ultrathin Films Made with Iron Phthalocyanine for Sensing

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

Piezoelectric biosensors for real-time monitoring of hybridization and detection of hepatitis C virus

The piezoelectric quartz crystal resonators modified with oligonucleotide probes were used for detection of hepatitis C virus (HCV) in serum. The gold electrodes on either rough or smooth surface crystals were modified with a self-assembled monolayer of cystamine. After activation with glutaraldehyde, either avidin or streptavidin were immobilized and used for attachment of biotinylated DNA probes (four different sequences). Piezoelectric biosensors were used in a flow-through setup for direct monitoring of DNA resulting from the reverse transcriptase-linked polymerase chain reaction (RT-PCR) amplification of the original viral RNA. The samples of patients with hepatitis C were analyzed and the results were compared with the standard RT-PCR procedure (Amplicor test kit of Roche, microwell format with spectrophotometric evaluation). The piezoelectric hybridization assay was completed in 10 min and the same sensing surface was suitable for repeated use. (C) 2004 Elsevier B.V. All rights reserved.

Ultrasonic material characterization using large-aperture PVDF receivers

This work describes the use of a large-aperture PVDF receiver in the measurement of liquid density and composite material elastic constants. The density measurement of several liquids is obtained with accuracy of 0.2% using a conventional NDE emitter transducer and a 70-mm-diameter, 52-mu m P(VDF-TrFE) membrane with gold electrodes. The determination of the elastic constants is based on the phase velocity measurement. Diffraction can lead to errors around 1% in velocity measurement when using alternatively the conventional pair of ultrasonic transducers (1-MHz frequency and 19-mm-diameter) operating in through-transmission mode, separated by a distance of 100 mm. This effect is negligible when using a pair of 10-MHz, 19-mm-diameter transducers. Nevertheless, the dispersion at 10 MHz can result in errors of about 0.5%, when measuring the velocity in composite materials. The use of an 80-mm diameter, 52-mu m-thick PVDF membrane receiver practically eliminates the diffraction effects in phase velocity measurement. The elastic constants of a carbon fiber reinforced polymer were determined and compared with the values obtained by a tensile test. (C) 2009 Elsevier B. V. All rights reserved.

Avaliação da limpeza de CDtrodo construídos a partir de CD de ouro gravável/fita adesiva de galvanoplastia

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

The use of Langmuir-Blodgett films of a perylene derivative and polypyrrole in the detection of trace levels of Cu2+ ions

Langmuir films of a tetracarboxylic perylene derivative and polypyrrole display condensed surface pressure isotherms that are shifted when Cu2+ ions are added to the ultrapure water subphase. These films were transferred onto interdigitated gold electrodes leading to Y-type Langmuir-Blodgett (LB) films. The electrodes modified with 5-layer LB films were immersed into a flask with ultrapure water and water containing Cu2+ ions at concentrations ranging from mM to muM. Impedance measurements indicated a distinct electrical response for the two types of films. Although the materials chosen have no specificity for ionic metals, they can be combined for detecting trace levels of Cu2+, which may be exploited in water quality monitoring. (C) 2004 Elsevier B.V. All rights reserved.

Structural and electrical properties of SrBi2Nb2O9 thin films prepared by chemical aqueous solution at low temperature

SrBi2Nb2O9 (SBN) thin films were prepared by the polymeric precursors method and deposited by dip coating onto Pt/Ti/SiO2/Si(100) substrates. The dip-coated films were specular and crack-free and crystallized during firing at 700 degrees C. Microstructure and morphological evaluation were followed by grazing incident X-ray diffraction (GIXRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The films exhibited somewhat porous grain structure with rounded grains of about 100 nm. For the electrical measurements, gold electrodes of 300 mu m in diameter were sputter deposited on the top surface, forming a metal-ferroelectric-metal (MFM) configuration. The remanent polarization (P-r) and coercive field (E-c) were 5.6 mu C/cm(2) and 100 kV/cm, respectively. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Relation between ambient humidity and ionic conductivity of poly(thionaphtheneindole): Behaviour as an amperometric humidity sensor

The electrical characteristics of oxidized poly(thionaphtheneindole) were investigated as a function of ambient relative humidity (r.h.). The current flowing through a pressed pellet of material between two massive gold electrodes plotted against voltage gives a wave-shaped curve with a halfwave potential at V = similar to 3 V. The current recorded at 4 V (plateau of the wave) is a sigmoidal function of r.h, with the inflexion point at similar to 60%. An interpretation of these findings is given, based on the influence of water on the dielectric constant of the material and on acid-base equilibrium between poly(thionaphtheneindole) and water, from which protons are produced. The behaviour of poly (thionaphtheneindole) as the active component of an amperometric humidity sensor is also reported.

Nanostructured films of perylene derivatives: High performance materials for taste sensor applications

Four perylene derivatives (PTCD) have been used as transducing materials in taste sensors fabricated with nanostructured Langmuir-Blodgett (LB) films deposited onto interdigitated gold electrodes. The Langmuir monolayers of PTCDs display considerable collapse pressures, with areas per molecule indicative of an edge-on or head-on arrangement for the molecules at the air/water interface. The sensing units for the electronic tongue were produced from 5-layer LB films of the four PTCDs, whose electrical response was characterized with impedance spectroscopy. The distinct responses of the PTCDs, attributed to differences in their molecular structures, allowed one to obtain a finger printing system that was able to distinguish tastes (salty, sweet, bitter and sour) at 1 μM concentrations, which, in some cases, are three orders of magnitude below the human threshold. Using Principal Component Analysis (PCA) data analysis, the electronic tongue also detected trace amounts of a pesticide and could distinguish among samples of ultrapure, distilled and tap water, and two brands of mineral water. © 2004 by American Scientific Publishers. All rights reserved.

Ultrasonic material characterization using diffraction-free PVDF receivers

This work describes the use of a large aperture PVDF receiver in the measurement of density of liquids and elastic constants of composite materials. The density measurement of several liquids is obtained with the accuracy of less than 0.2% using a conventional NDT emitter transducer and a 70-mm diameter, 52-μm P(VDF-TrFE) membrane with gold electrodes. The determination of the elastic constants of composite materials is based in the measurement of phase velocity. It is shown that the diffraction can lead to errors around 1% in the velocity measurement when using a pair of ultrasonic transducers (1MHz and 19mm diameter) operating in transmission-reception mode separated by a distance of 100 mm. This effect is negligible when using a pair of 10-MHz transducers. On the other hand, the dispersion at 10 MHz can result in errors of about 0.5%, measuring the velocity in composite materials. The use of an 80-mm diameter, 52-μm thick PVDF membrane receiver allows measuring the phase velocity without the diffraction effects.