FT-Raman, FTIR and density functional theory studies of a hydrogen-bonded formamide: pyridine complex

Raman and IR experiments have been carried out on formamide (FA) and pyridine (Py) mixtures at different compositions. The appearance of a new Raman band at 996 cm(-1) (nu(1) region of Py), whose intensity depends on the FA concentration, is assigned to an FA: Py adduct and this result is in excellent agreement with those of other authors who employed noisy light-based coherent Raman scattering spectroscopy (I((2)) CARS). Another band at 1587 cm(-1) (nu(8) region of Py) has been observed for the first time by using Raman and IR spectroscopies. Its intensity shows the same dependence on the FA concentration and this fact allows us to also attribute it to an FA: Py adduct. The good relationship between the Raman and IR data demonstrates the potential of the vibrational spectroscopy for this kind of study. Owing to higher absolute Raman scattering cross section, the nu(1) region of Py has been chosen for the quantitative analysis and a stoichiometry of 1 : 1 FA: Py is reported. The experimental data are very well supported by the density functional theory (OFT) calculation, which was employed for the first time to the present system. Furthermore, the actual investigation shows an excellent agreement with those reported from computational calculations for similar systems. A comparison with our previous studies confirms that: the solvent dielectric constant determines the stoichiometry of a given Lewis acid-base adduct in the infinite dilution limit. Copyright (C) 2009 John Wiley & Sons, Ltd.

Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Interaction of bovine serum albumin (BSA) with ionic surfactants evaluated by electron paramagnetic resonance (EPR) spectroscopy

EPR spectra of 5- and 16-doxyl stearic acid nitroxide probes (5-DSA and 16-DSA, respectively) bound to bovine serum albumin (BSA) revealed that in the presence of ionic surfactants, at least, two label populations coexist in equilibrium. The rotational correlation times (tau) indicated that component I displays a more restricted mobility state, associated to the spin labels bound to the protein; the less immobilized component 2 is due to label localization in the surfactant aggregates. For both probes, the increase of surfactant concentration leads to higher motional levels of component 1 followed by a simultaneous decrease of this fraction of nitroxides and its conversion into component 2. For 10 mM cethyltrimethylammonium chloride (CTAC), the nitroxides are 100% bound to the protein, whereas at 10mM N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and sodium dodecyl sulfate (SDS) the fractions of bound nitroxides are reduced to 18% and 86%, respectively. No significant polarity changes were observed in the whole surfactant concentration range for component 1. Moreover, at higher surfactant concentration, component 2 exhibited a similar polarity as in the pure surfactant micelles. For 16-DSA the surfactant effect is different: at 10mM of HPS and CTAC the fractions of bound nitroxides are 76% and 49%, respectively, while at 10 mM SDS they are present exclusively in a micellar environment, consistent with 100% of component 2. Overall, both SDS and HPS are able to effectively displace the nitroxide probes from the protein binding sites. while CTAC seems to affect the nitroxide binding to a significantly smaller extent. (C) 2008 Elsevier B.V. All rights reserved.

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.

Síntese e caracterização de TaC e óxido misto de tântalo e cobre nanoestruturados a partir do precursor oxálico de tântalo através de reações gás-sólido e sólido-sólido a baixa temperatura

The research and development of nanostructured materials have been growing significantly in the last years. These materials have properties that were significantly modified as compared to conventional materials due to the extremely small dimensions of the crystallites. The tantalum carbide (TaC) is an extremely hard material that has high hardness, high melting point, high chemical stability, good resistance to chemical attack and thermal shock and excellent resistance to oxidation and corrosion. The Compounds of Tantalum impregnated with copper also have excellent dielectric and magnetic properties. Therefore, this study aimed to obtain TaC and mixed tantalum oxide and nanostructured copper from the precursor of tris (oxalate) hydrate ammonium oxitantalato, through gas-solid reaction and solid-solid respectively at low temperature (1000 ° C) and short reaction time. The materials obtained were characterized by X-ray diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), Spectroscopy X-Ray Fluorescence (XRF), infrared spectroscopy (IR), thermogravimetric (TG), thermal analysis (DTA) and BET. Through the XRD analyses and the Reitiveld refinement of the TaC with S = 1.1584, we observed the formation of pure tantalum carbide and cubic structure with average crystallite size on the order of 12.5 nanometers. From the synthesis made of mixed oxide of tantalum and copper were formed two distinct phases: CuTa10O26 and Ta2O5, although the latter has been formed in lesser amounts

Síntese e caracterização de CuNb2O6 e CuNbC através de reação sólido- sólido e gás- sólido a baixa temperatura

The refractory metal carbides have proven important in the development of engineering materials due to their properties such as high hardness, high melting point, high thermal conductivity and high chemical stability. The niobium carbide presents these characteristics. The compounds of niobium impregnated with copper also have excellent dielectric and magnetic properties, and furthermore, the Cu doping increases the catalytic activity in the oxidation processes of hydrogen. This study aimed to the synthesis of nanostructured materials CuNbC and niobium and copper oxide from precursor tris(oxalate) oxiniobate ammonium hydrate through gas-solid and solid-solid reaction, respectively. Both reactions were carried out at low temperature (1000°C) and short reaction time (2 hours). The niobium carbide was produced with 5 % and 11% of copper, and the niobium oxide with 5% of copper. The materials were characterized by X-Ray Diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF), infrared spectroscopy (IR), thermogravimetric (TG) and differential thermal analysis (DTA , BET and particle size Laser. From the XRD analysis and Rietveld refinement of CuNbC with S = 1.23, we observed the formation of niobium carbide and metallic copper with cubic structure. For the synthesis of mixed oxide made of niobium and copper, the formation of two distinct phases was observed: CuNb2O6 and Nb2O5, although the latter was present in small amounts

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%.

Dielectric properties of thermosetting material nanocomposites

The dieletric relaxation properties of thermosetting material nanocomposites based on spherosilicate nanoplatforms were studied from room temperature to 170 degrees C, varying the frequency from 10 to 1000 KHz. Permittivity (epsilon'), dielectric loss (epsilon ''), and activation energy (E-a) were calculated. The results of dielectric relaxation were confirmed by those of the final properties. The dielectric loss amplitude decreases with increasing ODPG content until about 70-73 wt % and slightly increases at higher ODPG content. This means that the increasing of the ODPG content in the composite samples decreases the number of pendants groups and/or increases crosslink densitv, causing decreased motion of organic tethers, and subsequently decreasing of the dipolar mobility. The results of apparent activation energy, fracture toughness and tensile modulus mechanical properties show the same profile with respect to ODPG content, in the sense that they exhibit maxima around 70 wt % ODPG. For the ODPG/MDA composites, this formulation of 70 wt % ODPG containing excess of amine is not composition where the highest crosslinked density is reached. This implies that the best mechanical properties and E-a are provided by some degree of chain flexibility. (c) 2007 Wiley Periodicals, Inc.

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.

Descarga em barreira dielétrica: construção de um reator DBD e caracterização mediante análises ópticas e elétricas do plasma produzido

The plasma produced by Dielectric Barrier Discharge (DBD) is a promising technique for producing plasma in atmospheric pressure and has been highlighted in several areas, especially in biomedical and textile industry, this is due to the fact that the plasma generated by DBD not reaches high temperatures, enabling use it for thermally sensitive materials. But still it is necessary the development of research related to understanding of the chemical, physical and biological interaction between the non-thermal plasma at atmospheric pressure with cells, tissues, organs and organisms. This work proposes to develop equipment DBD and characterize it in order to obtain a better understanding of the process parameters of plasma production and how it behaves under the parameters adopted in the process, such as distance, frequency and voltage applied between electrodes. For this purpose two techniques were used to characterize distinct from each other. The first was the method of Lissajous figures, this technique is quite effective and accurately for complete electrical characterization equipment DBD. The second technique used was Optical Emission Spectroscopy (EEO) very effective tool for the diagnosis of plasma with it being possible to identify the excited species present in the plasma produced. Finally comparing the data obtained by the two techniques was possible to identify a set of parameters that optimize the production when combined DBD plasma atmosphere in the equipment was built precisely in this condition 0.5mm-15kV 600Hz, giving way for further work

Investigation of microwave dielectric relaxation solid state process in the antiferroelectric phase of NaNbO3 ceramics

This letter reports microwave dielectric measurements performed in the antiferroelectric phase of NaNbO3 ceramics from 100 to 450 K. Remarkable dielectric relaxation was found within the antiferroelectric phase and in the vicinity of the ferroelectric-antiferroelectric phase transition. Such dielectric relaxation process was associated with relaxations of polar nanoregions with strong relaxor-like characteristic. In addition, the microwave dielectric measurements also revealed an unexpected and unusual anomaly in the relaxation strength, which was related to a disruption of the antiferroelectric order induced by a possible AFE-AFE phase transition. (C) 2004 Elsevier Ltd. All rights reserved.