Electrochemical Oxidation of Hydroxylamine on Gold in Aqueous Acidic Electrolytes: An in Situ SERS Investigation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Surface structure and electronic properties of Pt-Fe/C nanocatalysts and their relation with catalytic activity for oxygen reduction

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

Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

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

Thermal evaporation furnace with improved configuration for growing nanostructured inorganic materials

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

Double-Tagging Polymerase Chain Reaction with a Thiolated Primer and Electrochemical Genosensing based on Gold Nanocomposite Sensor for Food Safety

A novel material for electrochemical biosensing based on rigid conducting gold nanocomposite (nano-AuGEC) is presented. Islands of chemisorbing material (gold nanoparticles) surrounded by nonreactive, rigid, and conducting graphite epoxy composite are thus achieved to avoid the stringent control of surface coverage parameters required during immobilization of thiolated oligos in continuous gold surfaces. The spatial resolution of the immobilized thiolated DNA was easily controlled by merely varying the percentage of gold nanoparticles in the composition of the composite. As low as 9 fmol (60 pM) of synthetic DNA were detected in hybridization experiments when using a thiolated probe. Moreover, for the first time a double tagging PCR strategy was performed with a thiolated primer for the detection of Salmonella sp., one of the most important foodborne pathogens affecting food safety. Ibis assay was performed by double-labeling the amplicon during the PCR with a -DIG and -SH set of labeled primers. The thiolated end allows the immobilization of the amplicon on the nano-AuGEC electrode, while digoxigenin allows the electrochemical detection with the antiDIG-HRP reporter in the femtomole range. Rigid conducting gold nanocomposite represents a good material for the improved and oriented immobilization of biomolecules with excellent transducing properties for the construction of a wide range of electrochemical biosensors such as immunosensors, genosensors, and enzymosensors.

Screen-Printed Carbon Electrode Modified with Poly-L-histidine Applied to Gold(III) Determination

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

NIR luminescent Er3+/Yb3+ co-doped SiO2-ZrO2 nanostructured planar and channel waveguides: Optical and structural properties

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

Arrays of gold microelectrodes made from split integrated circuit chips

A simple and inexpensive way to fabricate arrays of gold microelectrodes is proposed. Integrated circuit chips are sawed through their middle, normal to the longest axis, leading to destruction of the silicon circuit and rupture of the gold wires that interconnect it with the external terminals. Polishing the resulting rough surface converts the tips of the wires embedded in the chip halves into arrays of gold microdisks of about 25 mu m diameter. The number of active microelectrodes (MEs), of an array depends on the number of pins in the chip, n, being typically (n/2)-4. These MEs can be used individually or externally interconnected in any combination. X-ray images of the chips and micrographs of the resulting surface of the polished arrays have revealed variable distances between neighbor MEs, which are, however, larger than 10 times the radius of the disks. This feature of the MEs prevents diffusional cross-talk between electrodes. The use of these microdisk electrodes for analytical purposes exhibits sigmoidal voltammograms, and chronoamperometric experiments confirm the nonlinear i vs. t(1/2) plots, typical for processes where radial diffusion prevails. Satisfactory uniformity was observed for the response of each electrode of an array, indicating similarity of geometry and disk areas. The potentialities of these MEs were demonstrated by the determination of cadmium at ppb levels using square wave voltammetry with preconcentration. Due to the relative ease with which these MEs can be manufactured and their good performance in (chemical) analysis, wide applications in electrochemistry and electroanalysis is envisioned.

Surface-enhanced resonance Raman scattering as an analytical tool for single molecule detection

A perylene derivative, n-(n-butyl)-n'-(4-aminobutyl) perylene-3,4,9,10-tetracarboxylic acid diimide (simplified as nBu-PTCD-(CH2)(4)-NH2) has been chosen as the target molecule for studies involving single molecule detection (SMD) using Raman scattering. The enhancement of the Raman signal is the result of the multiplicative effects of two phenomena, resonance Raman scattering (RRS) and surface-enhanced Raman scattering (SERS), which leads to the resulting surface-enhanced resonance Raman scattering (SERRS) process. The SERRS spectra from a single molecule have been collected using both silver and gold colloids. The SMD detection of the fundamental vibrational frequencies characteristic of nBu-PTCD-(CH2)(4)-NH2 is complemented with the detection of some overtones and combinations from ring stretching modes at the single molecule level. The background characterization of the ensemble vibrational spectroscopy of the target perylene and its SERRS is also presented, which includes the UV-vis absorption, experimental and calculated Raman scattering and infrared absorption, and molecular organization using reflection-absorption infrared spectroscopy (RAIRS).

Nanostructured organic layers via polymer demixing for interface-enhanced photovoltaic cells

Significant progress is being made in the photovoltaic energy conversion using organic semiconducting materials. One of the focuses of attention is the morphology of the donor-acceptor heterojunction at the nanometer scale, to ensure efficient charge generation and loss-free charge transport at the same time. Here, we present a method for the controlled, sequential design of a bilayer polymer cell architecture that consists of a large interface area with connecting paths to the respective electrodes for both materials. We used the surface-directed demixing of a donor conjugated/guest polymer blend during spin coating to produce a nanostructured interface, which was, after removal of the guest with a selective solvent, covered with an acceptor layer. With use of a donor poly(p-phenylenevinylene) derivative and the acceptor C-60 fullerene, this resulted in much-improved device performance, with external power efficiencies more than 3 times higher than those reported for that particular material combination so far.

Effects of ion beam on nanoindentation characteristics of glassy polymeric carbon surface

Glassy polymeric carbon (GPC) is a useful material for medical applications due to its chemical inertness and biocompatible characteristics. Mitral and aortic and hydrocephalic valves are examples of GPC prosthetic devices that have been fabricated and commercialized in Brazil. In this work, ion beam was used to improve the mechanical characteristics of GPC surface and therefore to avoid the propagation of microcracks where the cardiac valves are more fragile. A control group of phenolic resin samples heat-treated at 300, 400, 700, 1000, 1500, and 2500 degrees C was characterized by measuring their hardness and Young's reduced elastic modulus with the depth of indentation. The control group was compared to results obtained with samples heat-treated at 700, 1000, and 1500 degrees C and bombarded with energetic ions of silicon, carbon, oxygen, and gold at energies of 5, 6, 8, and 10 MeV, respectively, with fluences between 10x10(13) and 10x10(16) ions/cm(2). GPC nonbombarded samples showed that hardness depends on the heat treatment temperature (HTT), with a maximum hardness for heat treatment at 1000 degrees C. The comparison between the control group and bombarded group also showed that hardness, after bombardment, had a greater increase for samples prepared at 700 degrees C than for samples prepared at higher temperatures. The Young's elastic modulus presents an exponential relationship with depth. The parameters obtained by fitting depend on the HTT and on the ion used in the bombardment more than on energy and fluence. The hardness results show clearly that bombardment can promote carbonization, increase the linkage between the chains of the polymeric material, and promote recombination of broken bonds in lateral groups that are more numerous for samples heat-treated at 700 degrees C. (c) 2004 Elsevier B.V. All rights reserved.

Flow-through cell based on an array of gold microelectrodes obtained from modified integrated circuit chips

The construction of a flow-through cell incorporating an array of gold microelectrodes is described and its application to flow injection analysis with amperometric detection is presented, Simple modification of almost any conventional integrated circuit chip, used as an inexpensive source of pre-assembled gold micro-wires, leads to the rapid and successful preparation of arrays of 8-48 elements, the polymeric encapsulation material from the top face of the chip is removed by abrasion until the gold micro-mires (used to interconnect the silicon circuit to the external contact pins of the chip) are disrupted and their transversal (elliptical) sections become exposed. Once polished, the flat and smooth top surface of the gold microelectrode-array chip (MEAC) is provided with a spacer and fitted under pressure against an acrylic block with the reference and auxiliary electrodes, to form the electrochemical (thin-layer) flow cell, while the contact pins are plugged into a standard IC socket, This design ensures autonomous electric contact with each electrode and allows fast dismantling for polishing or substitution, the performance of flow cells with MEACs was investigated utilizing the technique of reverse pulse amperometry without oxygen removal, A method was established for the determination of the copper concentration in sugar cane spirit, regulated by law for beverages, Samples from industrial producers and small-scale (alembic) brewers were compared, With a 24 MEAC, a detection limit of 30 mu g I-l of copper (4.7 x 10(-7) mol l(-1) of Cu-II for 100 mu l injections) was calculated, Routine operation was established at a frequency of 60-90 determinations per hour, Intercomparison with atomic absorption spectrometric determinations resulted in excellent agreement.

Gold electrodes from recordable CDs

Gold electrodes are widely used in electrochemistry and electroanalytical chemistry. The notable performance when used in stripping analysis of many ionic species and the extraordinary affinity of thio compounds for its surface make these electrodes very suitable for many applications. This paper reports a simple and novel way to construct gold electrodes (CDtrodes) using recordable CDs as the gold source. The nanometer thickness of the gold layer of recordable disks (50-100 mm) favors the construction of band nanoelectrodes with areas as small as 10(-6) cm(2). The plane surface can be easily used for the construction of conventional-sized gold electrodes for batch or now injection analysis or even to obtain electrodes as large as 100 cm(2). The low price of commercial recordable CDs allows a one way use. The evaluation and applicability of these electrodes in the form of nanoelectrodes, in batch and associated with flow cells, are illustrated in this paper.

Ga-Modified Nanostructured ZnO: Characterization and Application in Dye-Sensitized Solar Cells

ZnO has received great attention in many applications due to its electronic and optical properties. We report on the preparation of ZnO and gallium-containing ZnO (ZnO:Ga) nanoparticles by the precipitation method. The nanoparticles have the wurtzite structure and a high crystallinity. Gallium ions are present as Ga(3+), as evidenced by the binding energies through XPS. Porosity and surface area of the powder increased under increasing gallium level, explained by the smaller particle size of ZnO:Ga samples compared with ZnO. The estimated optical band gap of ZnO was 3.2 eV, comparable to ZnO:Ga.

Gold-bearing iron duricrust in Central Brazil

In the Cuiabá region-State of Mato Grosso, Central Brazil-primary gold mineralization is hosted by two generations of quartz veins in Precambrian metamorphic terrains of the Cuiabá Group. Gold is mined from the veins and mainly from the eluvial horizons that cover the deeply altered basement. In the lodes gold occurs as small particles (less than 1 mm) associated with pyrite and contains up to 5% Ag. Larger particles and nuggets of almost pure gold are found in the iron duricrust which caps the upper levels of the weathering profile. It is difficult to determine the average grade of this kind of deposit but some prospects in the Cuiabá region produce up to 2 g gold per ton of ore. Lateritization is responsible for both the formation of the iron crust and the concentration of gold within the regolith. Under a tropical climate, the supergene alteration of phyllites of the Cuiabá Group has led to the formation of a weathering profile consisting typically of saprolite, mottled clay zone and duricrust, from bottom to top. The duricrust is directly derived form the in situ weathering of phyllites. Geochemical balance calculations indicate that in the transition from the saprolite to the duricrust lateritization has promoted a progressive loss of Si, Al and K, and more than 500% of absolute Fe enrichment. Gold underwent a supergene evolution related to the development of the weathering profile. In the saprolite and mottled clay zone, associated with quartz and oxidized sulfides, gold dissolves as demonstrated by corrosion features at the surface of the particles. The formation of secondary gold in the duricrust is indicated by the larger size of the nuggets, their higher fineness and the close relationship between gold and the neoformed iron oxy-hydroxides. © 1991.