Porous silicon optical cavity structure applied to high sensitivity organic solvent sensor

The present work reports the thermal annealing process, the number of layer and electrochemical process effect in the optical response quality of Bragg and microcavity devices that were applied as organic solvent sensors. These devices have been obtained by using porous silicon (PS) technology. The optical characterization of the Bragg reflector, before annealing, showed a broad photonic band-gap structure with blue shifted and narrowed after annealing process. The electrochemical process used to obtain the PS-based device imposes the limit in the number of layers because of the chemical dissolution effect. The interface roughness minimizations in the devices have been achieved by using the double electrochemical cell setup. The microcavity devices showed to have a good sensibility for organic solvent detection. The thermal annealed device showed better sensibility feature and this result was attributed to passivation of the surface devices. (c) 2007 Elsevier Ltd. All rights reserved.

The role of quantum confinement and crystalline structure on excitonic lifetimes in silicon nanoclusters

The emission energy dependence of the photoluminescence (PL) decay rate at room temperature has been studied in Si nanoclusters (Si-ncl) embedded in Si oxide matrices obtained by thermal annealing of substoichiometric Si oxide layers Si(y)O(1-y), y=(0.36,0.39,0.42), at various annealing temperatures (T(a)) and gas atmospheres. Raman scattering measurements give evidence for the formation of amorphous Si-ncl at T(a)=900 degrees C and of crystalline Si-ncl for T(a)=1000 degrees C and 1100 degrees C. For T(a)=1100 degrees C, the energy dispersion of the PL decay rate does not depend on sample fabrication conditions and follows previously reported behavior. For lower T(a), the rate becomes dependent on fabrication conditions and less energy dispersive. The effects are attributed to exciton localization and decoherence leading to the suppression of quantum confinement and the enhancement of nonradiative recombination in disordered and amorphous Si-ncl. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3457900]

Comparative study of the adsorption and dissociation of vinylacetic acid and acrylic acid on silicon (001)

In this work, we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of acrylic acid (AAc) and vinylacetic acid (VAA) on the silicon surface. Our total energy calculations support the proposed experimental process, as it indicates that the chemisorption of the molecule is as follows: The gas phase VAA (AAc) adsorbs molecularly to the electrophilic surface Si atom and then dissociates into H(2)C = CH - COO and H, bonded to the electrophilic and nucleophilic surface silicon dimer atoms, respectively. The activation energy for both processes correspond to thermal activations that are smaller than the usual growth temperature. In addition, the electronic structure, calculated vibrational modes, and theoretical scanning tunneling microscopy images are discussed, with a view to contribute to further experimental investigations.

Structure of an Odorant-Binding Protein from the Mosquito Aedes aegypti Suggests a Binding Pocket Covered by a pH-Sensitive ""Lid""

Background: The yellow fever mosquito, Aedes aegypti, is the primary vector for the viruses that cause yellow fever, mostly in tropical regions of Africa and in parts of South America, and human dengue, which infects 100 million people yearly in the tropics and subtropics. A better understanding of the structural biology of olfactory proteins may pave the way for the development of environmentally-friendly mosquito attractants and repellents, which may ultimately contribute to reduction of mosquito biting and disease transmission. Methodology: Previously, we isolated and cloned a major, female-enriched odorant-binding protein (OBP) from the yellow fever mosquito, AaegOBP1, which was later inadvertently renamed AaegOBP39. We prepared recombinant samples of AaegOBP1 by using an expression system that allows proper formation of disulfide bridges and generates functional OBPs, which are indistinguishable from native OBPs. We crystallized AaegOBP1 and determined its three-dimensional structure at 1.85 angstrom resolution by molecular replacement based on the structure of the malaria mosquito OBP, AgamOBP1, the only mosquito OBP structure known to date. Conclusion: The structure of AaegOBP1 (= AaegOBP39) shares the common fold of insect OBPs with six alpha-helices knitted by three disulfide bonds. A long molecule of polyethylene glycol (PEG) was built into the electron-density maps identified in a long tunnel formed by a crystallographic dimer of AaegOBP1. Circular dichroism analysis indicated that delipidated AaegOBP1 undergoes a pH-dependent conformational change, which may lead to release of odorant at low pH (as in the environment in the vicinity of odorant receptors). A C-terminal loop covers the binding cavity and this ""lid"" may be opened by disruption of an array of acid-labile hydrogen bonds thus explaining reduced or no binding affinity at low pH.

Crystallographic characterization of silicon nitride ceramics sintered with Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) additions

Silicon nitride ceramics were sintered using Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) (E(2)O(3) denotes a mixed oxide Of Y(2)O(3) and rare-earth oxides) as sintering additives. The intergranular phases formed after sintering was investigated using high-resolution X-ray diffraction (HRXRD). The use of synchrotron radiation enabled high angular resolution and a high signal to background ratio. Besides the appearance Of beta-Si(3)N(4) phase the intergranular phases Y(3)Al(5)O(12) (YAG) and Y(2)SiO(5) were identified in both samples. The refinement of the structural parameters by the Rietveld method indicated similar crystalline structure Of beta-Si(3)N(4) for both systems used as sintering additive. On the other hand, the intergranular phases Y(3)Al(5)O(12) and Y(2)SiO(5) shown a decrease of the lattice parameters, when E(2)O(3) was used as additive, indicating the formation of solid solutions of E(3)Al(5)O(12) and E(2)SiO(5), respectively. (C) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

An Array Recursive Least-Squares Algorithm With Generic Nonfading Regularization Matrix

We present a novel array RLS algorithm with forgetting factor that circumvents the problem of fading regularization, inherent to the standard exponentially-weighted RLS, by allowing for time-varying regularization matrices with generic structure. Simulations in finite precision show the algorithm`s superiority as compared to alternative algorithms in the context of adaptive beamforming.

Synthesis, characterization and catalytic evaluation of cubic ordered mesoporous iron-silicon oxides

Iron was successfully incorporated in FDU-1 type cubic ordered mesoporous silica by a simple direct synthesis route. The (Fe/FDU-1) samples were characterized by Rutherford back-scattering spectrometry (RBS), small angle X-ray scattering (SAXS). N(2) sorption isotherm, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). The resulting material presented an iron content of about 5%. Prepared at the usual acid pH of -0.3, the composite was mostly formed by amorphous silica and hematite with a quantity of Fe(2+) present in the structure. The samples prepared with adjusted pH values (2 and 3.5) were amorphous. The samples` average pore diameter was around 12.0 nm and BET specific surface area was of 680 m(2) g(-1). Although the iron-incorporated material presented larger lattice parameter, about 25 nm compared to pure FDU-1, the Fe/FDU-1 composite still maintained its cubic ordered fcc mesoporous structure before and after the template removal at 540 degrees C. The catalytic performance of Fe/FDU-1 was investigated in the catalytic oxidation of Black Remazol B dye using a catalytic ozonation process. The results indicated that Fe/FDU-1 prepared at the usual acid pH exhibited high catalytic activity in the mineralization of this pollutant when compared to the pure FDU-1. Fe(2)O(3) and Fe/FDU-1 prepared with higher pH of 2 and 3.5. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis and structure of cage-like mesoporous silica using different precursors

In this work the synthesis of cubic, FDU-1 type, ordered mesoporous silica (OMS) was developed from two types of silicon source, tetraethyl orthosilicate (TEOS) and a less expensive compound, sodium silicate (Na(2)Si(3)O(7)), in the presence of a new triblock copolymer template Vorasurf 504 (EO(38)BO(46)EO(38)). For both silicon precursors the synthesis temperature was evaluated. For TEOS the effect of polymer dissolution in methanol and the acid solution (HCl and HBr) on the material structure was analyzed. For Na(2)Si(3)O(7) the influence of the polymer mass and the hydrothermal treatment time were the explored experimental parameters. The samples were examined by Small Angle X-ray Scattering (SAXS) and Nitrogen Sorption. For both precursors the decrease on the synthesis temperature from ambient, -25 degrees C, to -15 degrees C improved the ordered porous structure. For TEOS, the SAXS results showed that there is an optimum amount of hydrophobic methanol that contributed to dissolve the polymer but did not provoke structural disorder. The less electronegative Br-ions, when compared to Cl-, induced a more ordered porous structure, higher surface areas and larger lattice parameters. For Na(2)Si(3)O(7) the increase on the hydrothermal treatment time as well as the use of an optimized amount of polymer promoted a better ordered porous structure. (C) 2011 Elsevier B.V. All rights reserved.

Chemical bonding and composition of silicon nitride films prepared by inductively coupled plasma chemical vapor deposition

Thin silicon nitride films were prepared at 350 degrees C by inductively coupled plasma chemical vapor deposition on Si(100) substrates under different NH(3)/SiH(4) or N(2)/SiH(4) gas mixture. The chemical composition and bonding structure of the deposited films were investigated as a function of the process parameters, such as the gas flow ratio NH(3)/SiH(4) or N(2)/SiH(4) and the RF power, using X-ray photoelectron spectroscopy (XPS). The gas flow ratio was 1.4, 4.3, 7.2 or 9.5 and the RF power, 50 or 100 W. Decomposition results of Si 2p XPS spectra indicated the presence of bulk Si, under-stoichiometric nitride, stoichiometric nitride Si(3)N(4), oxynitride SiN(x)O(y), and stoichiometric oxide SiO(2), and the amounts of these compounds were strongly influenced by the two process parameters. These results were consistent with those obtained from N 1s XPS spectra. The chemical composition ratio N/Si in the film increased with increasing the gas flow ratio until the gas flow ratio reached 4.3, reflecting the high reactivity of nitrogen, and stayed almost constant for further increase in gas flow ratio, the excess nitrogen being rejected from the growing film. A considerable and unexpected incorporation of contaminant oxygen and carbon into the depositing film was observed and attributed to their high chemical reactivity. (C) 2010 Elsevier B.V. All rights reserved.

Oxygen-mediated electron transport through hybrid silicon-organic interfaces

We investigate from first principles the electronic and transport properties of hybrid organic/silicon interfaces of relevance to molecular electronics. We focus on conjugated molecules bonded to hydrogenated Si through hydroxyl or thiol groups. The electronic structure of the systems is addressed within density functional theory, and the electron transport across the interface is directly evaluated within the Landauer approach. The microscopic effects of molecule-substrate bonding on the transport efficiency are explicitly analyzed, and the oxygen-bonded interface is identified as a candidate system when preferential hole transfer is needed.

Structural-electronic aspects related to the near-infrared light emission of Fe-doped silicon films

The need of efficient (fast and low consumption) optoelectronic devices has always been the driving force behind the investigation of materials with new or improved properties. To be commercially attractive, however, these materials should be compatible with our current micro-electronics industry and/or telecommunications system. Silicon-based compounds, with their matured processing technology and natural abundance, partially comply with such requirements-as long as they emit light. Motivated by these issues, this work reports on the optical properties of amorphous Si films doped with Fe. The films were prepared by sputtering a Si+Fe target and were investigated by different spectroscopic techniques. According to the experimental results, both the Fe concentration and the thermal annealing of the samples induce changes in their atomic structure and optical-electronic properties. In fact, after thermal annealing at similar to 750 degrees C, the samples partially crystallize with the development of Si and/or beta-FeSi(2) crystallites. In such a case, certain samples present light emission at similar to 1500 nm that depends on the presence of beta-FeSi(2) crystallites and is very sensitive to the annealing conditions. The most likely reasons for the light emission (or absence of it) in the considered Fe-doped Si samples are presented and discussed in view of their main structural-electronic characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

Crystal structure of garciniaphenone and evidences on the relationship between keto-enol tautomerism and configuration

Garciniaphenone (=rel-(1R,5R,7R)-3-benzoyl-4-hydroxy-8,8-dimethyl-1,7-bis(3-methylbut-2-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione; 1). a novel natural product, was isolated from a hexane extract of Garcinia brasiliensis fruits. The crystal structure of 1 as well as the selected geometrical and Configurational features were compared with those of known related polyprenylated benzophenones. Garciniaphenone is the first representative of polyprenylated benzophenones without a prenyl substituent at C(5). Notably, the absence of a 5-prenyl substituent has an impact on the molecular geometry. The tautomeric form of 1 in the solid state was readily established by a residual-electronic-density map generated by means of a difference Fourier analysis, and there is an entirely delocalized six-membered chelate ring encompassing the keto-enol moiety. The configuration at C(7) was used to rationalize the nature of the keto-enol tautomeric form within 1. The intermolecular array in the network is maintained by nonclassical intermolecular H-bonds.

Dinuclear Azide-Bridged Copper(II) Complex as Building Block for the Assembly of a 2D-Supramolecular Array

A novel Schiff base-copper(II) complex [Cu(2)L(2)(N(3))(2)](ClO(4))(2) 1, where L = (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), containing azide-bridges between adjacent copper ions in a dinuclear arrangement was isolated and characterized both in the solid state and in solution by X-ray crystallography and different spectroscopic techniques. Azide binding constants were estimated from titrations of the precursor [CuL(H(2)O)(2)](2+) solutions with sodium azide, giving rise to the azido-bridged species, [Cu(2)L(2)(N(3))(2)](2+). Raman spectra showed asymmetric stretching band at 2060 cm(-1), indicating the presence of azido ligands with a symmetric mu(1,) (1) binding geometry. EPA spectra, in frozen methanol/water solutions at 77 K, exhibited characteristic features of copper centers in tetragonal pyramidal coordination geometry, exhibiting magnetic interactions between them. Further, in solid state, two different values for magnetic coupling in this species were obtained, J/k = -(5.14 +/- 0.02) cm(-1) attributed to the mu(1, 1) azide-bridge mode, and J`z`/k = -(2.94 +/- 0.11) cm(-1) for the interaction between dinuclear moieties via water/perchorate bridges. Finally, an attempt was made to correlate structure and magnetic data for this dinuclear asymmetric end-on azido bridged-copper(II) 1 complex with those of another correlated dinuclear system, complex [Cu(2)L(2)Cl(2)](ClO(4))(2) 2, containing the same tridentate diimine ligand, but with chloro-bridged groups between the copper centres.

Local Structure and Photochromic Response in Ormosils Containing Dodecatungstophosphoric Acid

Two hybrid materials based on dodecatungstophosphoric acid (HPW) dispersed in ormosils modified with 3-aminopropiltrietoxysilane (APTS) or with N-(3-(trimethoxysilyl)-propyl)-ethylene-diamine (TSPEN) show reversible photochromic response induced by irradiation in the 200-390 nm UV range. A set of solid-state nuclear magnetic resonance (NMR) techniques was used to analyze the structural properties of the main components of these hybrids (the HPW polyanion, the inorganic matrix, and the organic functionalities). For the ormosils, the use of (29)Si NMR, {(1)H}-(29)Si cross-polarization, and {(1)H}-(29)Si HETCOR revealed a homogeneous distribution of silicon species Q ``, T(2), and T(3) for the APTS hybrid, contrasting with the separation of T(3) species in the TSPEN hybrid. The combination of (31)P NMR, {(1)H}-(31)P cross-polarization and (31)P-{(1)H} spin-echo double resonance (SEDOR) revealed the dispersion of the HPW ions in the ormosil, occupying sites with a high number of close protons (>50). Differences in the molecular dynamics at room temperature, inferred from SEDOR experiments, indicate a state of restricted mobility of the HPW ion and the surrounding molecular groups in the TSPEN hybrid. This behavior is consistent with the presence of more amino groups in the TSPEN, acting as chelating groups to the HPW ion. This hybrid, with the strong chelate interaction of the diamine group, shows the most intense photochromic response, in agreement with the charge transfer models proposed to explain the photochromic effect. Electronic reflectance spectroscopy in irradiated samples revealed the presence of one-electron and two-electron reduced polyanions. The one-electron reduced species could be detected also by (31)P NMR spectroscopy immediately after UV irradiation.

Evaluation of the dental structure loss produced during maintenance and replacement of occlusal amalgam restorations

The aim of this in vitro study was to evaluate four different approaches to the decision of changing or not defective amalgam restorations in first primary molar teeth concerning the loss of dental structure. Ditched amalgam restorations (n = 11) were submitted to four different treatments, as follows: Control group - polishing and finishing of the restorations were carried out; Amalgam group - the ditched amalgam restorations were replaced by new amalgam restorations; Composite resin group - the initial amalgam restorations were replaced by composite resin restorations; Flowable resin group - the ditching around the amalgam restorations was filled with flowable resin. Images of the sectioned teeth were made and the area of the cavities before and after the procedures was determined by image analysis software to assess structural loss. The data were submitted to ANOVA complemented by the Student Newman Keuls test (p < 0.05). The cavities in all the groups presented significantly greater areas after the procedures. However, the amalgam group showed more substantial dental loss. The other three groups presented no statistically significant difference in dental structure loss after the re-treatments. Thus, replacing ditched amalgam restorations by other similar restorations resulted in a significant dental structure loss while maintaining them or replacing them by resin restorations did not result in significant loss.