Direct Observation of Tetragonal Distortion in Epitaxial Structures through Secondary Peak Split in a Synchrotron Radiation Renninger Scan

This paper reports a direct observation of an interesting split of the (022)(022) four-beam secondary peak into two (022) and (022) three-beam peaks, in a synchrotron radiation Renninger scan (phi-scan), as an evidence of the layer tetragonal distortion in two InGaP/GaAs (001) epitaxial structures with different thicknesses. The thickness, composition, (a perpendicular to) perpendicular lattice parameter, and (01) in-plane lattice parameter of the two epitaxial ternary layers were obtained from rocking curves (omega-scan) as well as from the simulation of the (022)(022) split, and then, it allowed for the determination of the perpendicular and parallel (in-plane) strains. Furthermore, (022)(022) omega:phi mappings were measured in order to exhibit the multiple diffraction condition of this four-beam case with their split measurement.

AFM analysis of bleaching effects on dental enamel microtopography

The purpose of this in vitro study was to test a new methodology to evaluate the effects of 35% hydrogen peroxide agent on the microtopography of sound enamel using an atomic force microscope (AFM). The buccal sound surfaces of three extracted human lower incisors were used, without polishing the surfaces to maintain them with natural morphology. These unpolished surfaces were subjected to bleaching procedure with 35% hydrogen peroxide that consisted of 4 applications of the bleaching agent on enamel surfaces for 10 min each application. Surface images were obtained in a 15 mu m x 15 mu m area using an AFM. The roughness (Ra and RMS) and the power spectral density (PSD) were obtained before and after the bleaching treatment. As results we could inquire that the PSD analyses were very suitable to identifying the morphological changes on the surfaces, while the Ra and RMS parameters were insufficient to represent the morphological alterations promoted by bleaching procedure on enamel. The morphological wavelength in the range of visible light spectrum(380-750 nm) was analyzed, showing a considerable increase of the PSD with the bleaching treatment. (C) 2009 Elsevier B. V. All rights reserved.

Surface and Quantum Confinement Effects in ZnO Nanocrystals

ZnO nanocrystals are studied using theoretical calculations based on the density functional theory. The two main effects related to the reduced size of the nanocrystals are investigated: quantum confinement and a large surface:volume ratio. The effects of quantum confinement are studied by saturating the surface dangling bonds of the nanocrystals with hypothetical H atoms. To understand the effects of the surfaces of the nanocrystals, all saturation is removed and the system is relaxed to its minimum energy position. Several different surface motifs are reported, which should be observed experimentally. Spin-polarized calculations are performed in the nonsaturated nanocrystals, leading to different magnetic moments. We propose that this magnetic moment can be responsible for the intrinsic magnetism observed in ZnO nanostructures.

Size effects on silver nanoparticles` properties

In this work a systematic study of the dependence of the structural, electronic, and vibrational properties on nanoparticle size is performed. Based on our total energy calculations we identified three characteristic regimes associated with the nanoparticle`s dimensions: (i) below 1.5 nm (100 atoms) where remarkable molecular aspects are observed; (ii) between 1.5 and 2.0 nm (100 and 300 atoms) where the molecular behavior is influenced by the inner core crystal properties; and (iii) above 2.0 nm (more than 300 atoms) where the crystal properties are preponderant. In all considered regimes the nanoparticle`s surface modulates its properties. This modulation decreases with the increasing of the nanoparticle`s size.

Effects of torsional disorder on poly-para-phenylene

We study the effect of thermal disorder on the electronic structure of one-dimensional poly-para-phenylene (PPP). In a real chain the torsion angles between rings are bound to be distributed over a range of values, which depend on temperature, and thus the chain is intrinsically disordered. In this study we simulated this kind of thermally induced off-diagonal disorder through the simple Huckel method. We base our Hamiltonian on ab initio results for the effect of temperature on torsion angles, and the effect of torsion angles on the energy gap. We analyze the electronic structure of 200-monomer-long chains focusing on the density of states, and the associated localization character (measured by the inverse participation ratio). Our results contrast with the usually assumed Gaussian-shaped density of localized states for disordered systems. (C) 2009 Elsevier B.V. All rights reserved.

Interparticle Interactions Effects on the Magnetic Order in Surface of Fe(3)O(4) Nanoparticles

We report interparticle interactions effects on the magnetic structure of the surface region in Fe(3)O(4) nanoparticles. For that, we have studied a desirable system composed by Fe(3)O(4) nanoparticles with (d) = 9.3 nm and a narrow size distribution. These particles present an interesting morphology constituted by a crystalline core and a broad (similar to 50% vol.) disordered superficial shell. Two samples were prepared with distinct concentrations of the particles: weakly-interacting particles dispersed in a polymer and strongly-dipolar-interacting particles in a powder sample. M(H, T) measurements clearly show that strong dipolar interparticle interaction modifies the magnetic structure of the structurally disordered superficial shell. Consequently, we have observed drastically distinct thermal behaviours of magnetization and susceptibility comparing weakly- and strongly-interacting samples for the temperature range 2 K < T < 300 K. We have also observed a temperature-field dependence of the hysteresis loops of the dispersed sample that is not observed in the hysteresis loops of the powder one.

Confinement and surface effects in B and P doping of silicon nanowires

Several experimental groups have achieved effective n- and p-type doping of silicon nanowires (SiNWs). However, theoretical analyses on ultrathin SiNWs suggest that dopants tend to segregate to their surfaces, where they would combine with defects such as dangling bonds (DB), becoming electronically inactive. Using fully ab initio calculations, we show that the differences in formation energies among surface and core substitutional sites decrease rapidly as the diameters of the wires increase, indicating that the dopants will be uniformly distributed. Moreover, occurrence of the electronically inactive impurity/DB complex rapidly becomes less frequent for NWs of larger diameters. We also show that the high confinement in the ultrathin SiNWs causes the impurity levels to be deeper than in the silicon bulk, but our results indicate that for NWs of diameters larger than approximately 3 nm the impurity levels recover bulk characteristics. Finally, we show that different surfaces will lead to different dopant properties in the gap.

Photo-irradiation effects on the surface morphology of poly(p-phenylene vinylene) films

In this work, we have studied the surface morphology of photo-irradiated poly(p-phenylene vinylene) (PPV) thin films by using atomic force microscopy (AFM). We have analyzed the first-order statistical parameters, the height distribution and the distance between selected peaks. The second-order statistical analysis was introduced calculating the auto-covariance function to determine the correlation length between heights. We have observed that the photo-irradiation process produces a surface topology more homogeneous and isotropic such as a normal surface. In addition, the polymer surface irradiation can be used as a new methodology to obtain materials optically modified. (C) 2009 Elsevier B.V. All rights reserved.

Molecular Ordering in Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy: The Effects of Drying Procedures

Sum-Frequency Vibrational Spectroscopy (SFVS) has been used to investigate the effect of nitrogen-flow drying on the molecular ordering of Layer-by-Layer (LbL) films of poly(allylamine hydrochloride) (PAH) alternated with poly(styrene sulfonate) (PSS). We find that films dried by spontaneous water evaporation are more ordered and homogeneous than films dried by nitrogen flow. The latter are quite inhomogeneous and may have regions with highly disordered polymer conformation. We propose that drying by spontaneous water evaporation reduces the effect of drag by the drying front, while during nitrogen-flow drying the fast evaporation of water ""freezes"" the disordered conformation of adsorbed polyelectrolyte molecules. These findings are important for many applications of LbL films, since device performance usually depends on film morphology and its molecular structure.

Spin-polarization effects in homogeneous and non-homogeneous diluted magnetic semiconductor heterostructures

Spin polarization is a key characteristic in developing spintronic devices. Diluted magnetic heterostructures (DMH), where subsequent layers of conventional and diluted magnetic semiconductors (DMS) are alternate, are one of the possible ways to obtain it. Si being the basis of modern electronics, Si or other group-IV DMH can be used to build spintronic devices directly integrated with conventional ones. In this work we study the physical properties and the spin-polarization effects of p-type DMH based in group-IV semiconductors (Si, Ge, SiGe, and SiC), by performing self-consistent (k) over right arrow . (p) over right arrow calculations in the local spin density approximation. We show that high spin polarization can be maintained in these structures below certain values of the carrier concentrations. Full spin polarization is attained in the low carrier concentration regime for carrier concentrations in the DMS layer up to similar to 2.0 x 10(19) cm(-3) for Si and up to similar to 6.0 x 10(19) cm(-3) for SiC. Partial, but still important spin polarization can be achieved for all studied group-IV DMH, with the exception of Ge for carrier concentrations up to 6.0 x 10(19) cm(-3). The role played by the effective masses and the energy splitting of the spin-orbit split-off hole bands is also discussed throughout the paper.

The effects of temperature on the molecular orientation of zinc phthalocyanine films

Phthalocyanine compounds have been widely investigated as candidate materials for technological applications, which is mainly due to their thermal stability and possibility of processing in the form of thin films. In most applications, the controlled growth of thin films with high crystalline quality is essential. In this study, zinc phthalocyanine (ZnPc) thin films were prepared by evaporation on glass and Au-coated glass substrates with subsequent annealing at different temperatures in ambient atmosphere. The morphological and structural features of 80 nm thick zinc phthalocyanine films were investigated, evidencing an alpha -> beta phase transformation after annealing the films at 200 A degrees C, as indicated by UV-Vis spectroscopy and FTIR analyses. A better uniformity of the annealed films was also evidenced via AFM analysis, which may be of importance for applications where film homogeneity and excellent optical quality are required.

Adhesion as a tool for in-built nanotechnology design in cementitious materials

Confined water, such as those molecules in nanolayers of 2-3 nm in length, plays an important role in the adhesion of hydrophilic materials, mainly in cementitious ones. In this study, the effects of water containing kosmotropic substances on adhesion, known for their ability of enhancing the hydrogen bond (H-bond) network of confined water, were evaluated using mechanical strength tests. Indeed, to link adhesion provided by water confined in nanolayers to a macro-response of the cementitious samples, such as the bending strength, requires the evaluation of local water H-bond network configuration in the presence of kosmotropes, considering their influences on the extent and the strength of H-bonds. Among the kosmotropes, trimethylamine and sucrose provided a 50% increase in bending strength compared to the reference samples, the latter just using water as an adhesive, whereas trehalose was responsible for reducing the bending strength to a value close to the samples without any adhesive. The results attained opened up perspectives regarding exploring the confined water behavior which naturally occurs throughout the hydration process in cement-based materials.

Protein Adsorption onto Polyelectrolyte Layers: Effects of Protein Hydrophobicity and Charge Anisotropy

Ellipsometry was used to investigate the influence of ionic strength (I) and pH on the adsorption of bovine serum albumin (BSA) or beta-lactoglobulin (BLG) onto preabsorbed layers of two polycations: poly(diallyldimethylammonium chloride) (PDADMAC) or poly(4-vinylpyridine bromide) quaternized with linear aliphatic chains of two (QPVP-C2) or five (QPVP-C5) carbons. Comparisons among results for the three polycations reveal hydrophobic interactions, while comparisons between BSA and BLG-proteins of very similar isoelectric points (pI)-indicate the importance of protein charge anisotropy. At pH close to pI, the ionic strength dependence of the adsorbed amount of protein (Gamma) displayed maxima in the range 10 < I < 25 mM corresponding to Debye lengths close to the protein radii. Visualization of protein charge by Delphi suggested that these ionic strength conditions corresponded to suppression of long-range repulsion between polycations and protein positive domains, without diminution of short-range attraction between polycation segments and locally negative protein domains, in a manner similar to the behavior of PE-protein complexes in solution.(1-4) This description was consistent with the disappearance of the maxima at pH either above or below pI. In the former case, Gamma values decrease exponentially with I(1/2), due to screening of attractions, while in the latter case adsorption of both proteins decreased at low I due to strong repulsion. Close to or below pI both proteins adsorbed more strongly onto QPVP-C5 than onto QPVP-C2 or PDADMAC due to hydrophobic interactions with the longer alkyl group. Above pI, the adsorption was more pronounced with PDADMAC because these chains may assume more loosely bound layers due to lower linear charge density.

Effects of hydroxyl group distribution on the reactivity, stability and optical properties of fullerenols

We investigate the impact of hydroxyl groups on the properties of C(60)(OH)(n) systems, with n = 1, 2, 3, 4, 8, 10, 16, 18, 24, 32 and 36 by means of first-principles density functional theory calculations. A detailed analysis from the local density of states has shown that adsorbed OH groups can induce dangling bonds in specific carbon atoms around the adsorption site. This increases the tendency to form polyhydroxylated fullerenes (fullerenols). The structural stability is analyzed in terms of the calculated formation enthalpy of each species. Also, a careful examination of the electron density of states for different fullerenols shows the possibility of synthesizing single molecules with tunable optical properties.

Interaction of giant extracellular Glossoscolex paulistus hemoglobin (HbGp) with zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS): Effects of oligomeric dissociation

The present work focuses on the interaction between the zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp). Electronic optical absorption, fluorescence emission and circular dichroism spectroscopy techniques, together with Gel-filtration chromatography, were used in order to evaluate the oligomeric dissociation as well as the autoxidation of HbGp as a function of the interaction with HPS. A peculiar behavior was observed for the HPS-HbGp interaction: a complex ferric species formation equilibrium was promoted, as a consequence of the autoxidation and oligomeric dissociation processes. At pH 7.0, HPS is more effective up to 1 mM while at pH 9.0 the surfactant effect is more intense above 1 mM. Furthermore, the interaction of HPS with HbGp was clearly less intense than the interaction of this hemoglobin with cationic (CTAC) and anionic (SDS) surfactants. Probably, this lower interaction with HPS is due to two factors: (i) the lower electrostatic attraction between the HPS surfactant and the protein surface ionic sites when compared to the electrostatic interaction between HbGp and cationic and anionic surfactants, and (ii) the low cmc of HPS, which probably reduces the interaction of the surfactant in the monomeric form with the protein. The present work emphasizes the importance of the electrostatic contribution in the interaction between ionic surfactants and HbGp. Furthermore, in the whole HPS concentration range used in this study, no folding and autoxidation decrease induced by this surfactant were observed. This is quite different from the literature data on the interaction between surfactants and tetrameric hemoglobins, that supports the occurrence of this behavior for the intracellular hemoglobins at low surfactant concentration range. Spectroscopic data are discussed and compared with the literature in order to improve the understanding of hemoglobin-surfactant interaction as well as the acid isoelectric point (pI) influence of the giant extracellular hemoglobins on their structure-activity relationship. (c) 2007 Elsevier B.V. All rights reserved.