Preparation and characterization of erbium and ytterbium co-doped sol-gel SiO2 : HfO2 films for planar waveguides

This work reports on the preparation of erbium and ytterbium co-doped SiO2:HfO2 single mode planar waveguides using the sol-gel method. Silica nanoparticles were prepared from tetraethylorthosilicate in basic media and the films were characterized by transmission electron microscopy, scanning electron microscopy, mechanical profilometry, M-lines spectroscopy based on prism coupling technique, X-ray diffractometry, infrared spectroscopy and photoluminescence spectroscopy. The film thicknesses and the refractive indexes were adjusted in order to satisfy a future efficient coupling to single mode optical fiber. Films suitable for both weak and strong light confinement were prepared varying hafnia concentration into the silica matrix. The lifetime values of erbium I-4(13/2) state were measured in order to investigate the influence of clustering and hydroxyl groups on the fluorescence quantum efficiency of the I-4(13/2) level, responsible for the emission at 1.55 mu m attributed to the I-4(13/2) -> I-4(15/2) transition. The high lifetime values suggest the absence of erbium clusters and the elimination of hydroxyl groups by rapid thermal process. (c) 2007 Elsevier B.V. All rights reserved.

The electrochemical cleavage of the nitrobenzoyl group from butyl nitrobenzoates in N,N-dimethylformamide

The applicability of the nitrobenzoyl group [NO2C6H4CO-] to protecting the functional hydroxyl group was investigated through study of the electrochemical behaviour of the butyl 4-, 3- and 2-nitrobenzoate compounds. These isomers are reduced in two cathodic steps. The first, at potentials of ca. -0.9 V vs. SCE, is attributed to the formation of rather stable anion radicals, involving one-electron transfer. The second, at potentials of ca. -1.7 V vs. SCE, occurs with a two-electron transfer in an ECE process, in which the dianion produced undergoes scission of the C-O bond giving n-butanoate ions with high yields (similar to 80%)

Density improvement of the sol-gel dip-coated SnO2 films by chemical surface modification

We compare the effect of organic (Tiron (R)) and inorganic (Mn(11)) additives on the low temperature (< 600 degrees C) densification of the sol-gel dip-coated SnO2 films. The structural and compositional properties of the samples were investigated by X-ray reflectometry (XRR), X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The results suggest that the replacement of hydroxyl groups at the particle surface by Tiron (R) reduces the level of agglomeration of the sol, increasing the particles packing and the apparent density of the coatings. Undoped and Mn-doped films drawn from a Tiron (R) containing suspension show after firing at 500 degrees C a porosity reduction of 12 and 8.6%, respectively. The porosity decrease is less pronounced (4.3%) for the film without additives. Both XAS and XPS data show the presence of trivalent manganese. The formation of a non-homogeneous solid solution characterised by the presence of Mn(111) replacing tin atom near to the crystallite surface was evidenced by XAS. Additionally, XPS results reveal the presence of metallic Sn at the surface of films containing Tirono. (c) 2005 Elsevier Ltd. All rights reserved.

Nanostructure and luminescent properties of sol-gel derived europium-doped amine functionalised hybrids

The effect of doping by europium triflate on the nanoscopic structure of organic-inorganic hybrid formed by a siliceous network containing pendant amine-terminated propyl chains, called aminosils, was investigated by Small-Angle X-ray Scattering (SAXS). It appears that the composites exhibit a two-level structure. The first level consists of well-condensed cubic-like siloxane octamers, with a radius of gyration around 2 angstrom. The second level is formed by the aggregation of these siloxane nanodomains to form larger structures, in which the nanodomains are spatially correlated and separated by the organic pendant chains. Europium doping inhibits the aggregation between siloxane octamers, leading to a less compact second-level structure. This can be explained by the Eu3+ stop coordination close to the external surface of the siloxane nanodomains, as detected by luminescence spectroscopy.

Electronic and structural properties of the (10(1)over-bar0) and (11(2)over-bar0) ZnO surfaces

The structural and electronic properties of ZnO (10 (1) over bar0) and (11 (2) over bar0) surfaces were investigated by means of density functional theory applied to periodic calculations at B3LYP level. The stability and relaxation effects for both surfaces were analyzed. The electronic and energy band properties were discussed on the basis of band structure as well as density of states. There is a significant relaxation in the (10 (1) over bar0) as compared to the (11 (2) over bar0) terminated surfaces. The calculated direct gap is 3.09, 2.85, and 3.09 eV for bulk, (10 (1) over bar0), and (11 (2) over bar0) surfaces, respectively. The band structures for both surfaces are very similar.

Thermogravimetric and UV-vis spectroscopic studies of chromium redox reactions in rutile pigments

In this study undoped and Cr, Sb or Mo doped TiO(2) were synthesized by polymeric precursor method and characterized by X-ray diffraction, UV-VIS spectroscopy, infrared spectroscopy and thermogravimetry (TG). The TG curves showed a continuous mass loss assigned to the hydroxyl elimination and Cr(6+) reduction. Doped TiO(2) samples showed a higher mass loss assigned to water and gas elimination at lower temperatures. In these doped materials a decrease in the anatase-rutile phase transition temperature was observed. After calcination at 1,000 A degrees C, rutile was obtained as a single phase material without the presence of Cr(6+).

A joint computational and experimental study of a novel dioxomolybdenum(VI) complex bearing chiral N,N-dimethyllactamide ligand

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

Theoretical study on the reaction mechanism of VO2+ with propyne in gas phase

Possible molecular mechanisms of the gas-phase ion/molecule reaction of VO2+ in its lowest singlet and triplet states ((1)A(1)/(3)A '') with propyne have been investigated theoretically by density functional theory (DFT) methods. The geometries, energetic values, and bonding features of all stationary and intersystem crossing points involved in the five different reaction pathways (paths 1-5), in both high-spin (triplet) and low-spin (singlet) surfaces, are reported and analyzed. The oxidation reaction starts by a hydrogen transfer from propyne molecule to the vanadyl complex, followed by oxygen migration to the hydrocarbon moiety. A hydride transfer process to the vanadium atom opens four different reaction courses, paths 1-4, while path 5 arises from a hydrogen transfer process to the hydroxyl group. Five crossing points between high- and low-spin states are found: one of them takes place before the first branching point, while the others occur along path 1. Four different exit channels are found: elimination of hydrogen molecule to yield propynaldehyde and VO+ ((1)Sigma/(3)Sigma); formation of propynaldehyde and the moiety V-(OH2)(+); and two elimination processes of water molecule to yield cationic products, Prod-fc(+) and Prod-dc(+) where the vanadium atom adopts a four- and di-coordinate structure, respectively.

Luminescent nano-composites generated from a spray

The spray-pyrolysis (SP) synthesis technique has been employed to obtain SiO2:Eu3+ and gamma-AlOOH:Eu3+, It was possible to obtain sub-micrometric spherical particles of SiO2 with luminescent Eu3+ ions bonded to the silica surface or embedded in amorphous silica beads, by controlling the synthesis and annealing process. Boehmite y-AlOOH doped with Eu3+ nanoparticles were synthesized by SP at moderate temperature (200 degrees C) with Eu3+ ions bonded to the surface hydroxyls of the boehmite nanocrystals. Luminescent nanocomposites were obtained by controlled reaction of gamma-AlOOH:Eu3+ nanocrystals with ASN (asparagine). In these nano-composites, the Eu3+ are held at the surface of the boehmite nanocrystals and partially shielded from interactions with additional luminescence quenchers (hydroxyl groups, water molecules). (C) 2008 Elsevier B.V. All rights reserved.

Synthesis and electrochemical behavior of single-crystal magnetite nanoparticles

Water-dispersed magnetite nanoparticle synthesis from iron(II) chloride in dimethyl sulfoxide (DMSO)-water solution at different DMSO-water ratios in alkaline medium was reported. TEM and XRD results suggest a single-crystal formation with mean particle size in the range 4-27 nm. Magnetic nanoparticles are formed by the oxidative hydrolysis reaction from green rust species that leads to FeOOH formation, followed by autocatalysis of the adsorbed available Fe(II) on the FeOOH surfaces. The available hydroxyl groups seem to be dependent on the DMSO-water ratio due to strong molecular interactions presented by the solvent mixture. Goethite phase on the magnetite surface was observed by XRD data only for sample synthesized in the absence of DMSO. In addition, cyclic voltammetry with carbon paste electroactive electrode (CV-CPEE) results reveal two reduction peaks near 0 and +400 mV associated with the presence of iron(III) in different chemical environments related to the surface composition of magnetite nanoparticles. The peak near +400 mV is related to a passivate thin layer surface such as goethite on the magnetite nanoparticle, assigned to the intensive hydrolysis reaction due to strong interactions between DMSO-water molecules in the initial solvent mixture that result in a hydroxyl group excess in the medium. Pure magnetite phase was only observed in the samples prepared at 30% (30W) and 80% (80W) water in DMSO in agreement with the structured molecular solvent cluster formation. The goethite phase present on the, magnetite nanoparticle surface like a thin passivate layer only was detectable using CV-CPEE, which is a very efficient, cheap, and powerful tool for surface characterization, and it is able to determine the passivate oxyhydroxide or oxide thin layer presence on the nanoparticle surface.

Role of polyethylene-graft-glycidyl methacrylate compatibilizer on the biodegradation of poly(epsilon-calprolactone)/cellulose acetate blends

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

pH changes at the surface of root dentin when using root canal sealers containing calcium hydroxide

The purpose of this study was to investigate long-term pH changes in cavities prepared in root surface dentin of extracted teeth after obturation of the root canal with gutta-percha and a variety of sealers containing calcium hydroxide. After cleaning and shaping, root canals in 50 recently extracted, human single-rooted teeth were divided into five groups. Each of four groups was obturated with gutta-percha and either Sealapex, Sealer 26, Apexit, or CRCS, all of which contain calcium hydroxide. The remaining group served as the control and was not obturated with gutta-percha or sealer. Cavities were prepared in the facial surface of the roots in the cervical and middle regions. The pH was measured in these dentinal cavities at the initiation of the experiment, and 3, 7, 14, 21, 28, 45, 60, 90, and 120 days after obturation. Results indicate that the pH at the surface of the root does not become alkaline when calcium hydroxide cements are used as root canal sealers. Regardless of the sealer used, the observed pattern of pH change was not different from that seen in the control group of roots that were not treated with sealer. It is concluded that calcium hydroxide-containing cements, although suitable for use as root canal sealants, do not produce an alkaline pH at the root surface. If such a pH change is related to treatment of root resorption, these sealants do not contribute to this treatment. Copyright © 1996 by The American Association of Endodontists.

Changes in pH at the dentin surface in roots obturated with calcium hydroxide pastes

The purpose of this study was to determine the pH, after defined periods of time, in cavities prepared in the facial surface of the cervical, middle, and apical regions of roots obturated with calcium hydroxide pastes. Root canal instrumentation was performed on 40 recently extracted, single-rooted human teeth. Cavities 1.5 mm in diameter and 0.75 mm in depth were prepared in the cervical, middle, and apical regions of the facial surface of each root. Teeth were randomly divided into four groups. One group was left unobturated and served as a control. The three remaining groups were obturated with either aqueous calcium hydroxide, calcium hydroxide mixed with camphorated monochlorophenol, or Pulpdent pastes. Access cavities and apical foramina were closed with Cavit. Each tooth was stored individually in a vial containing unbuffered isotonic saline. pH at the surface was measured in the cervical, middle, and apical cavities at 0 and 3, 7, 14, 21, 28, 45, 60, 90, and 120 days. Results indicate that hydroxyl ions derived from calcium hydroxide pastes diffused through root dentin at all regions over the experimental period of 120 days. The pattern of pH change at the tooth surface was similar in all regions of the root, regardless of the type of calcium hydroxide paste used. This was a rapid rise in pH from a control value of pH 7.6, to greater than pH 9.5 by 3 days, followed by a small decline to pH 9.0 over the next 18 days, before finally rising and remaining at, or above pH 10.0 for the remainder of the experimental period. Pulpdent paste in the apical region was the only exception in this pattern, producing a pH rise nearly one full unit below the other pastes, pH 9.3. These results indicate that, for all pastes tested, a high pH is maintained at the root surface for at least 120 days. Copyright © 1996 by The American Association of Endodontists.

Caries and its association with infant feeding and oral health-related behaviours in 3-4-year-old Brazilian children

Objectives: To investigate the relationships between socio-demographic factors, infant feeding habits, oral hygiene and the prevalence and patterns of caries in Brazilian 3-4-year-olds. Methods: Systematic random sampling was used to select children enrolled in municipal nurseries in Araraquara, Brazil, in 1998. Clinical examinations were carried out by one examiner using dmft and dmfs indices and WHO criteria. Questionnaires for information related to the socio-demographic background, oral hygiene and dietary history of the children were completed by their mothers. Results: Caries was seen in 46% of the children; 17% of them had the more extensive pattern involving molars and incisors. Social class, mother's education, and age at which breast-feeding terminated showed statistically significant associations with caries. Feeding bottles with added sugars were still being given to 80% of the children. When the significant variables were taken into account only age at which breast-feeding terminated showed a significant relationship to the pattern of disease. Children who were never breast-fed or were breast-fed beyond the age of 24 months had a higher prevalence of the more extensive pattern of caries. Conclusions: The association between the length of time a mother breast-feeds and extensive caries should be a consideration in any local infant feeding policies or health promotion strategies. The duration for appropriate breast- or bottle-feeding should be emphasised.

Laparoscopic evaluation and treatment of the impalpable testis

Objectives: To evaluate the laparoscopic technique as a diagnostic and therapeutic tool in the management of patients with impalpable testis. Material and Methods: Fifty-nine patients with mean age of 6.3 years underwent laparoscopy to evaluate 85 impalpable testes that were classified as absent, canalicular and intra-abdominal. In the case of testicular absence, the procedure was terminated. In the case of canalicular testis, open inguinal exploration was performed. In intra-abdominal testis, either laparoscopic orchiopexy or orchiectomy was performed. According to the length of the vascular pedicle, orchipexy was performed either with or without vascular ligature. Post-operatively, the treated testes were evaluated according to size and location in the scrotum. Results: Seventeen (20%) of the 85 impalpable testes were diagnosed as absent, 21 (24.7%) as canalicular and 47 (55.3%) as intra-abdominal. Of the canalicular testes, 20 were explored by inguinotomy and one by laparoscopy. All the intra-abdominal testes were treated initially by laparoscopy, four being removed due to atrophy, 31 submitted to vascular ligature and 12 to primary orchipexy. Of those submitted to vascular ligature, 22 underwent a second stage orchipexy, of which 18 laparoscopically and 4 by inguinotomy. Of the 18 testes brought to the scrotum by staged laparoscopic orchipexy, 15 (83.3%) presented normal characteristics in the late follow-up, while of the 12 submitted to primary laparoscopic orchipexy, 8 (66.6%) were normal. There were no perioperative or late complications. Conclusions: Laparoscopy is a minimally invasive procedure with low morbidity that enables precise diagnosis of the impalpable testes. When intra-abdominal testes are found, either immediate laparoscopic orchiectomy, or primary and staged orchipexy are possible, with results equivalent to open procedures, with the advantage of smaller surgical incisions and shorter postoperative recovery.