Investigation of Iron (III) desferrioxamine B oxalate ligand exchange by UV-vis spectroscopy: the next step in developing a quantitative analytical method for measuring bioavailable iron in marine ecosystems

To date there are no analytical techniques designed to exclusively measure bioavailable iron in marine environments. The goal of this research is to develop such a technique by isolating the bioavailable iron using the terrestrial siderophore desferrioxamine B (DFB). This project contained many challenging aspects, but the specific goal of this study was to develop a robust analytical technique for quantification of Fe(III)-DFB complexes at nanomolar concentrations. Past work showed that oxalate (Ox) promotes photodissociation of Fe(III)-DFB to Fe(Il), and we are specifically interested in the mechanism of this process. A model was developed using known thermodynamic constants for Fe(III)-DFB and Fe(III) oxalato complexes and adjusting for ionic strength. The model was confirmed by monitoring the UV-VIS absorbance of the system at a variety of oxalate concentrations and pH. The model did not include ternary complexes. Next., the rate of Fe(1I) production during UV irradiation was examined. The results showed that the rate of Fe(II) production was based entirely on the [Fe(Ox)?]3- speciation, and that reoxidation of Fe(II) occurred via reactive oxygen intermediates. This reoxidation could be avoided by either decreasing the oxygen concentration or by adding a Fe(II) stabilizing reagent, such as ferrozine. Further studies need to be done to confirm that these results apply at sub nanomolar concentrations, and the issue of Fe(II) reoxidation at lower Fe concentrations needs to be addressed.

Determination of potassium and sodium in an ash sample by gamma-ray spectroscopy

Neutron activation analysis and gamma-ray spectroscopy were used to determine the quantity of potassium and sodium in an ash sample of Tabebuia sp bombarded with thermal neutrons. These techniques, widely applied in nuclear physics, can be used in the context of wood science as an alternative for the usual physical chemistry methods applied in this area. The quantity of K and Na in an 8.60 +/- 0.10 mg of ash was determined as being 1.3 +/- 0.3 mg and 11.0 +/- 1.8 mu g, respectively. The ratio of Tabebuia sp converted into ash was also determined as 0.758 +/- 0.004%.

Use of near-infrared Raman spectroscopy to detect IgG and IgM antibodies against Toxoplasma gondii in serum samples of domestic cats

Near-infrared Raman spectroscopy (NIRS) is a particularly promising technique that is being used in recent years for many biomedical applications. Optical spectroscopy has gained increasing prominence as a tool for quantitative analysis of biological samples, clinical diagnostic, concentration measurements of blood metabolites and therapeutic drugs, and analysis of the chemical composition of human tissues. Toxoplasmosis is an important zoonosis in public health, and domestic cats are the most important transmitters of the disease. This disease can be detected by several serological tests, which usually have a high cost and require a long time. The goal of this work was to investigate a new method to diagnosis Toxoplasma gondii infections using NIRS. In order to confirm antibody detection, 24 cat blood scrum samples were analyzed by the Raman spectra, from which 23 presented positive serology to toxoplasmosis and one was a reference negative serum. Characteristic Raman peaks allowed differentiation between negative and positive sera, confirming the possibility of antibody detection by Raman spectroscopy. These results give the first evidence that this technique can be useful to quantify antibodies in cat sera.

Mapping of adhesion forces on soil minerals in air and water by atomic force spectroscopy (AFS)

The adhesion force between an atomic force microscope (AFM) tip and sample surfaces, mica and quartz substrates, was measured in air and water. The force curves show that the adhesion has a strong dependence on both the surface roughness and the environmental conditions surrounding the sample. The variability of the adhesion force was examined in a series of measurements taken at the same point, as well as at different places on the sample surface. The adhesion maps obtained from the distribution of the measured forces indicated regions contaminated by either organic compounds or adsorbed water. Using simple mathematical expressions we could quantitatively predict the adhesion force behavior in both air and water. The experimental results are in good agreement with theoretical calculations, where the adhesion forces in air and water were mostly associated with capillary and van der Waals forces, respectively. A small long-range repulsive force is also observed in water due to the overlapping electrical double-layers formed on both the tip and sample surfaces.

Exploiting the versatility of taste sensors based on impedance spectroscopy

The versatility of sensor arrays made from nanostructured Langmuir-Blodgett (LB) and layer-by-layer (LBL) films is demonstrated in two ways. First, different combinations of sensing units are employed to distinguish the basic tastes, viz. sweet, sour, bitter, and salty tastes, produced, respectively, by small concentrations (down to 0.01 g/mol) of sucrose, HCl, quinine, and NaCl solutions. The sensing units are comprised of LB and/or LBL films from semiconducting polymers, a ruthenium complex, and sulfonated lignin. Then, sensor arrays were used to identify wines from different sources, with the high distinguishing ability being demonstrated in principal component analysis (PCA) plots. Particularly important was the fact that the sensing ability does not depend on specific interactions between analytes and the film materials, but a judicious choice of materials is, nevertheless, required for the materials to respond differently to a given sample. It is also shown that the interaction with the analyte may affect the morphology of the nanostructured films, as indicated with scanning electron microscopy. For instance, in wine analysis these changes are not irreversible and the original film morphology is retrieved if the sensing unit is washed with copious amounts of water, thus allowing the sensor unit to be reused.

Detection of glucose and triglycerides using information visualization methods to process impedance spectroscopy data

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

Micro-Raman spectroscopy and SEM/EDX applied to improve the zircon fission track method used for dating geological formations

The zircon mineral is widely studied in geochronology. In the case of the fission track method (FTM), the age is determined by the density of fission tracks at the zircon surface, which can be observed with an optical microscope after an appropriate chemical treatment (etching). The etching must be isotropic at the zircon grain surface to be used in the FTM, which leads those zircon grains whose etching is anisotropic to be discarded. The only reason for this discarding is the nonuniform morphology of the surface grain seen by optical microscopy, that is, no further physicochemical analysis is performed. In this work, combining micro-Raman and scanning electron microscopy (SEM) to study the etching anisotropy, it was shown that zircon grains that present at least one area at the surface where the density of fission track is uniform can be used in the FTM. The micro-Raman showed characteristic spectra of the standard zircon sample either from the areas where there are tracks or from where there are not. The only difference found was in the Raman bandwidths, which were broader for the areas with higher density of fission tracks. This suggests simply a decrease in the relative percentage of the crystalline/amorphous phases at these areas. The SEM/energy dispersive spectrometry (EDX) showed that there were no significant differences in the principal chemical composition at the areas with and without fission tracks. Copyright (c) 2008 John Wiley & Sons, Ltd.

Molecular and morphological characterization of bis benzimidazo perylene films and surface-enhanced phenomena

Thin solid films of bis benzimidazo perylene (AzoPTCD) were fabricated using physical vapor deposition (PVD) technique. Thermal stability and integrity of the AzoPTCD PVD films during the fabrication (similar to 400 degrees C at 10(-6) Torr) were monitored by Raman scattering. Complementary thermogravimetric results showed that thermal degradation of AzoPTCD occurs at 675 degrees C. The growth of the PVD films was established through UV-vis absorption spectroscopy, and the surface morphology was surveyed by atomic force microscopy (AFM) as a function of the mass thickness. The AzoPTCD molecular organization in these PVD films was determined using the selection rules of infrared absorption spectroscopy (transmission and reflection-absorption modes). Despite the molecular packing, X-ray diffraction revealed that the PVD films are amorphous. Theoretical calculations (density functional theory, B3LYP) were used to assign the vibrational modes in the infrared and Raman spectra. Metallic nanostructures, able to sustain localized surface plasmons (LSP) were used to achieve surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF).

Analysis of the Al-PANI interfaces by complex impedance spectroscopy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.

Anelastic spectroscopy in SmBa2Cu3O7

The possibility of variable stoichiometry and the high mobility of oxygen in the CuOx planes of SmBa2Cu3O7 give rise to a rich phase diagram. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature can distinguish among the different atomic jumps, which occur in the various phases or at different local ordering. In this paper, it is reported anelastic relaxation measurements in SmBa2Cu3O7, above room temperature, using a torsion pendulum operating in frequencies around 40 Hz. The mobility of oxygen atoms in the CuOx planes in the various phases has been discussed and the thermally activated peak of elastic energy dissipation observed around 500 K was interpreted in that framework. (C) 2004 Elsevier B.V. All rights reserved.

Measurement of oxygen atom diffusion in Nb and Ta by anelastic spectroscopy

Impurity interstitial atoms present in metals with BCC structure can diffuse in the metallic matrix by jumps to energetically equivalent crystallographic sites. Anelastic spectroscopy (internal friction) is based on the measurement of mechanical loss or internal friction as a function of temperature. Due to its selective and nondestructive nature, anelastic spectroscopy is well suited for the study of diffusion of interstitial elements in metals. Internal friction measurements were made using the torsion pendulum technique with oscillation frequency of a few Hz, temperature interval from 300 to 700 K, heating rate of about 1 K/min, and vacuum better than 10-5 mbar. The polycrystalline Nb and Ta samples used were supplied by Aldrich Inc. The results obtained showed thermally activated relaxation structures due to stress-induced ordering of oxygen atoms around the Nb (or Ta) atoms of the metallic matrix. The results were interpreted by three methods and led to activation enthalpy values for the diffusion of oxygen in Nb and Ta of 1.15 eV and 1.10 eV, respectively.

Dynamical Elastic Moduli of the Ti-13Nb-13Zr biomaterial alloy by mechanical spectroscopy

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

Determination of the oxygen and nitrogen interstitial diffusion coeficient in niobium by mechanical spectroscopy

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

Anelastic spectroscopy in a Ti alloy used as biomaterial

Ti and its alloys have been used thoroughly in the production of prostheses and dental implants due to their properties, such as high corrosion resistance, low elasticity modulus and high mechanical strength/density relation. Among the Ti-based alloys, the Ti-35Nb-7Zr-5Ta (TNZT) is one that presents the smallest elasticity modulus, making it an excellent alternative to be used as a biomaterial. In this paper, mechanical spectroscopy measurements were made in TNZT alloys containing several quantities of oxygen and nitrogen in solid solution. Mechanical spectroscopy measurements were made by using a torsion pendulum, operating at an oscillation frequency in the interval 4-30 Hz, temperature in the range 100-700 K, heating rate of about 1 K/min and vacuum lower than 10(-5) Torr. Complex relaxation structures and a reduction in the elasticity modulus were observed for the heat-treated and doped samples. The observed peaks were associated with the interactions of interstitial atoms and the alloy elements. (C) 2009 Elsevier B.V. All rights reserved.