Evidences for charge-transfer complex formation in the benzene adsorption on sulfated TiO2-a resonance Raman spectroscopy investigation

Benzene adsorbed on highly acidic sulfated TiO2 (S-TiO2) shows an intriguing resonance Raman (RR) effect, with excitation in the blue-violet region. There are very interesting spectral features: the preferential enhancement of the e(2g) mode (1595 cm(-1)) in relation to the a(1g) mode (ring-breathing mode at 995 cm(-1)) and the appearance of bands at 1565 and 1514 cm(-1). The band at 1565 cm(-1) is probably one of the components of the e(2g) split band, originally a doubly degenerate mode (8a, 8b) in neat benzene, and the band at 1514 cm(-1) is assigned to the 19a mode, an inactive mode in neat benzene. These facts indicate a lowering of symmetry in adsorbed benzene, which may be caused by a strong interaction between S-TiO2 and the benzene molecule with formation of a benzene to Ti (IV) charge transfer (CT) complex or by the formation of a benzene radical cation species. However, the RR spectra of the adsorbed benzene cannot be assigned to the benzene radical cation because the observed wavenumber of the ring-breathing mode does not have the value expected for this species. Moreover, it was found by ESR measurements that the amount of radicals was very low, and so it was concluded that a CT complex is the species that originates the RR spectra. The most favorable intensification of the band at 1595 cm(-1) in the RR spectra of benzene/S-TiO2 at higher excitation energy corroborates this hypothesis, as an absorption band in this energy range, assigned to a CT transition, is observed. Copyright (C) 2008 John Wiley & Sons, Ltd.

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.

A Study of the Effect of Nitrogen and Air Plasma Immersion Ion Implantation Treatments on the Properties of Carbon Fiber

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

Interfacial fracture of dentin adhesively bonded to quartz-fiber reinforced composite

The paper presents the results of an experimental study of interfacial failure in a multilayered structure consisting of a dentin/resin cement/quartz-fiber reinforced composite (FRC). Slices of dentin close to the pulp chamber were sandwiched by two half-circle discs made of a quartz-fiber reinforced composite, bonded with bonding agent (All-bond 2, BISCO, Schaumburg) and resin cement (Duo-link. BISCO, Schaumburg) to make Brazil-nut sandwich specimens for interfacial toughness testing. Interfacial fracture toughness (strain energy release rate, G) was measured as a function of mode mixity by changing loading angles from 0 degrees to 15 degrees. The interfacial fracture surfaces were then examined using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX) to determine the failure modes when loading angles changed. A computational model was also developed to calculate the driving forces, stress intensity factors and mode mixities. Interfacial toughness increased from approximate to 1.5 to 3.2 J/m(2) when the loading angle increases from approximate to 0, 0 to 15 degrees. The hybridized dentin/cement interface appeared to be tougher than the resin cement/quartz-fiber reinforced epoxy. The Brazil-nut sandwich specimen was a suitable method to investigate the mechanical integrity of dentin/cement/FRC interfaces. (C) 2011 Elsevier B.V. All rights reserved.

Abelianized obstruction for fixed points of fiber-preserving maps of surface bundles

Let f: M -> M be a fiber-preserving map where S -> M -> B is a bundle and S is a closed surface. We study the abelianized obstruction, which is a cohomology class in dimension 2, to deform f to a fixed point free map by a fiber-preserving homotopy. The vanishing of this obstruction is only a necessary condition in order to have such deformation, but in some cases it is sufficient. We describe this obstruction and we prove that the vanishing of this class is equivalent to the existence of solution of a system of equations over a certain group ring with coefficients given by Fox derivatives.

Analysis of the ethidium bromide bound to DNA by photoacoustic and FTIR spectroscopy

Under physiological conditions B-form DNA is an exceedingly stable structure. However, experimental evidences obtained through nuclear magnetic resonance and fluorescence anisotropy suggest that the structure of the double helix fluctuates substantially. We describe photoacoustic phase modulation frequency measurements of ethidium bromide (Eb) with calf thymus, DNA. As in fluorescence phase modulation measurements, we used an intercalating dye as a probe; however, we monitored the triplet excited state lifetime at different ionic strengths. The triplet lifetime of Eb varied from about 0.30 ms, with no DNA present, to 20 ms, (at a DNA:Eb molar ratio of 5). With salt titration, this value falls, to about 2.0 ms. This result suggests, a strong coupling between the phenantridinium ring of the ethidium and the base pairs because of the stacking movement of the DNA molecule under salt effect. This, effect may be understood considering DNA as a polyelectrolyte. The counterions, in the solution shield the phosphate groups, reducing the electrostatic repulsion force between them, hence compacting the DNA molecule. The results from Fourier transform infrared demonstrated two important bands: 3187 cm(-1) corresponding to the symmetric stretching of the NH group of the bases, and 1225 cm(-1) corresponding to the asymmetric stretching of phosphate groups shifted toward higher wavenumbers, suggesting a proximity between the intercalant and base pairs and a modification of the DNA backbone state, both induced by salt accretion.

Anelastic spectroscopy in Al2O3

Engineering ceramics have found use in many applications, such as engine parts, ball bearings, artificial bone and hip replacements and gyroscopes, because of their good chemical inertness, hardness, high temperature stability and excellent wear resistance. Oxide ceramic may meet these demands. Alumina (Al2O3) ceramics offer a high potential for many engineering applications, such as wear- and/or corrosion-resistant components, and as material for substrates or housings in microelectronic devices. Alumina is used among other things for seal ring, draw-cones, guides, water mixing tapes, bearing parts, medical prostheses and cutting tools. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature can distinguish among the different atomic jumps, which occurs in the various phases or at different local ordering. In this paper, it is reported anelastic relaxation measurements in Al2O3 samples using commercial starch. These measurements were carried out in a torsion pendulum operating in frequencies around 40 Hz. The results shown strongly influence of the type of forming in the elastic modulus obtained by anelastic relaxation measurements.

β-lactam antibiotics epitope mapping with STD NMR spectroscopy: A study of drug-human serum albumin interaction

Molecular recognition events are key issues in many biological processes. STD NMR (saturation transfer difference nuclear magnetic resonance spectroscopy) is one of the techniques used to understand such biological interactions. Herein, we have investigated the interactions of four β-lactam antibiotics belonging to two classes (cephalosporins and penicillins) with human serum albumin (HSA) by 1H STD NMR revealing that the interaction between the aromatic moiety and HSA is responsible for the binding efficiency. Thus, the structural differences from the five to six-membered thio ring in penicillins and cephalosporins do not seem to influence antibiotic-albumin interactions. © 2012 Sociedade Brasileira de Química.

Ultra-structural mapping of sugarcane bagasse after oxalic acid fiber expansion (OAFEX) and ethanol production by Candida shehatae and Saccharomyces cerevisiae

Background: Diminishing supplies of fossil fuels and oil spills are rousing to explore the alternative sources of energy that can be produced from non-food/feed-based substrates. Due to its abundance, sugarcane bagasse (SB) could be a model substrate for the second-generation biofuel cellulosic ethanol. However, the efficient bioconversion of SB remains a challenge for the commercial production of cellulosic ethanol. We hypothesized that oxalic-acid-mediated thermochemical pretreatment (OAFEX) would overcome the native recalcitrance of SB by enhancing the cellulase amenability toward the embedded cellulosic microfibrils. Results: OAFEX treatment revealed the solubilization of hemicellulose releasing sugars (12.56 g/l xylose and 1.85 g/l glucose), leaving cellulignin in an accessible form for enzymatic hydrolysis. The highest hydrolytic efficiency (66.51%) of cellulignin was achieved by enzymatic hydrolysis (Celluclast 1.5 L and Novozym 188). The ultrastructure characterization of SB using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy, Fourier transform-near infrared spectroscopy (FT-NIR), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) revealed structural differences before and after OAFEX treatment with enzymatic hydrolysis. Furthermore, fermentation mediated by C. shehatae UFMG HM52.2 and S. cerevisiae 174 showed fuel ethanol production from detoxified acid (3.2 g/l, yield 0.353 g/g; 0.52 g/l, yield, 0.246 g/g) and enzymatic hydrolysates (4.83 g/l, yield, 0.28 g/g; 6.6 g/l, yield 0.46 g/g). Conclusions: OAFEX treatment revealed marked hemicellulose degradation, improving the cellulases ability to access the cellulignin and release fermentable sugars from the pretreated substrate. The ultrastructure of SB after OAFEX and enzymatic hydrolysis of cellulignin established thorough insights at the molecular level. © 2013 Chandel et al; licensee BioMed Central Ltd.

Nucleation of superconductivity in a thin disk with a ring-like defect

We report on the influence of a circular defect on the vortex configuration in a mesoscopic superconducting sample. Effects associated with the pinning force of the circular defect on the configuration and on the vortex entry fields are studied for a very thin disk. We calculate the magnetization loop, vorticity, free energy and superconducting electrons for the disk in presence of an external magnetic field applied perpendicular to the disk plane. The magnetization curves are hysteretic, with paramagnetic response in part of the downward branch, also, in this part we found a vortex-anti-vortex state. © 2013 World Scientific Publishing Company.

Cytotoxic non-aromatic B-ring flavanones from Piper carniconnectivum C. DC.

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

Vibrational spectroscopy for probing molecular-level interactions in organic films mimicking biointerfaces

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

All-loop infrared-divergent behavior of most-subleading-color gauge-theory amplitudes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Vector Mode Analysis of Ring-Core Fibers: Design Tools for Spatial Division Multiplexing

Design tools have existed for decades for standard step-index fibers, with analytical expressions for cutoff conditions as a function of core size, refractive indexes, and wavelength. We present analytical expressions for cutoff conditions for fibers with a ring-shaped propagation region. We validate our analytical expressions against numerical solutions, as well as via asymptotic analysis yielding the existing solutions for standard step-index fiber. We demonstrate the utility of our solutions for optimizing fibers supporting specific eigenmode behaviors of interest for spatial division multiplexing. In particular, we address large mode separation for orbital angular momentum modes and fibers supporting only modes with a single intensity ring.

Multiscale sensing of antibody - antigen interactions by organic transistors and single-molecule force spectroscopy

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