Synthesis of hybrid silicates containing porphyrins incorporated by a sol-gel process and their properties

Porphyrin was incorporated in a silicate network, via a covalent bond, by grafting a functional group with 3-aminopropyltriethoxysilane, using a sol-gel process. We have carried out the synthesis and measured the absorption spectra, nuclear magnetic resonance spectra, infrared (IR) spectra, luminescence spectra and lifetime of these hybrid silicates, porphyrinosilicas. These samples contained the following free-base porphyrins: meso-tetrakis-p-chlorobenzoylporphyrin, meso-tetrakis-2,6-dichloro-3-chlorosulfonylphenylporphyrin. The obtained porphyrinosilicas have similar absorption and luminescence spectra to the free base porphyrins in solution. IR spectra confirm the formation of monomeric species. Lifetime measurement for porphyrinosilica reveals that 32% +/- 2% of porphyrin is covalently bonded to the silica network. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Nanoscale manipulation of CdSe quantum dots in layer-by-layer films: influence of the host polyelectrolyte on the luminescent properties

Thioglycolic acid-capped Use quantum dots (QDs) were assembled on glass substrates with two distinct polyelectrolytes, viz poly(allylamine hydrochloride) (PAH) and poly(amidoamine) (PAMAM), generation 4 dendrimer, via the layer-by-layer (LbL) technique. Films containing up to 30 polyelectrolyte/QD bilayers were prepared. The growth of the multilayers was monitored with UV-vis spectroscopy, which showed an almost linear increase in the absorbance of the 2.8 nm QDs at 535 nm with the number of deposited bilayers. AFM measurements estimated a film thickness of 3 nm per bilayer for the PAH/Cdse films. The adsorption process and the optical properties of the PAMAM/CdSe LbL films were further analyzed layer-by-layer using surface plasmon resonance (SPR), from which a thickness of 3.2 nm was found for a PAMAM/CdSe bilayer. Photoluminescence measurements revealed higher photooxidation of the quantum dots in PAH/CdSe than in PAMAM/CdSe films. (c) 2004 Elsevier B.V. All rights reserved.

Catechol biosensing using a nanostructured layer-by-layer film containing Cl-catechol 1,2-dioxygenase

dThe detection of aromatic compounds from pesticides and industrial wastewater has become of great interest, since these compounds withstand chemical oxidation and biological degradation, accumulating in the environment. In this work, a highly sensitive biosensor for detecting catechol was obtained with the immobilization of Cl-catechol 1,2-dioxygenase (CCD) in nanostructured films. CCD layers were alternated with poly(amidoamine) generation 4 (PAMAM G4) dendrimer using the electrostatic layer-by-layer (LbL) technique. Circular dichroism (CD) measurements indicated that the immobilized CCD preserved the same conformation as in solution. The thickness of the very first CCD layers in the LbL films was estimated at ca. 3.6 nm, as revealed by surface plasmon resonance (SPR). PAMAM/CCD 10-bilayer films were employed in detecting diluted catechol solutions using either an optical or electrical approach. Due to the mild immobilization conditions employed, especially regarding the pH and ionic strength of the dipping solutions, CCD remained active in the films for periods longer than 3 weeks. The optical detection comprised absorption experiments in which the formation of cis-cis muconic acid, resulting from the reaction between CCD and catechol, was monitored by measuring the absorbance at 260 nm after film immersion in catechol solutions. The electrical detection was carried out using LbL films deposited onto gold-interdigitated electrodes immersed in aqueous solutions at different catechol concentrations. Using impedance spectroscopy in a broad frequency range (1Hz-1kHz), we could detect catechol in solutions at concentrations as low as 10(-10) M. (c) 2005 Elsevier B.V. All rights reserved.

Mapping QTLs on chicken chromosome 1 for performance and carcass traits in a broiler x layer cross

With the objective of mapping quantitative trait loci (QTLs) for performance and carcass traits, an F-2 chicken population was developed by crossing broiler and layer lines. A total of 2063 F-2 chicks in 21 full-sib families were reared as broilers and slaughtered at 42 days of age. Seventeen performance and carcass traits were measured. Parental (F-0) and F-1 individuals were genotyped with 80 microsatellites from chicken chromosome 1 to select informative markers. Thirty-three informative markers were used for selective genotyping of F-2 individuals with extreme phenotypes for body weight at 42 days of age (BW42). Based on the regions identified by selective genotyping, seven full-sib families (649 F-2 chicks) were genotyped with 26 markers. Quantitative trait loci affecting body weight, feed intake, carcass weight, drums and thighs weight and abdominal fat weight were mapped to regions already identified in other populations. Quantitative trait loci for weights of gizzard, liver, lungs, heart and feet, as well as length of intestine, not previously described in the literature were mapped on chromosome 1. This F-2 population can be used to identify novel QTLs and constitutes a new resource for studies of genes related to growth and carcass traits in poultry.

Unusual interactions binding iron tetrasulfonated phthalocyanine and poly(allylamine hydrochloride) in layer-by-layer films

Molecular-level interactions are found to bind iron tetrasulfonated phthalocyanine (FeTsPc) and the polyelectrolyte poly(allylamine hydrochloride) (PAH) in electroactive layer-by-layer (LBL) films. These interactions have been identified by comparing Fourier transform infrared (FTIR) and Raman spectroscopy data from bulk samples of FeTsPc and PAH with those from FeTsPc/PAH LBL films. of particular importance were the SO3- -NH3 interactions that we believe to bind PAH and FeTsPc and the interactions between unprotonated amine groups of PAH and the coordinating metal of the phthalocyanine. The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the Q band of FeTsPc at 676 nm. Film thickness estimated with profilometry was ca. I I Angstrom per bilayer for films adsorbed on glass. Reflection absorption infrared spectroscopy (RAIRS) revealed an anisotropy in the LBL film adsorbed on gold with FeTsPc molecules oriented perpendicularly to the substrate plane. Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 1.07 and 0.81 V, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/Ag+). The peak shape and current dependence on the scan rate suggest that the process is a diffusion controlled charge transport. In the presence of dopamine, the electroactivity of FeTsPc/PAH LBL films vanishes due to a passivation effect. Dopamine activity is not detected either because the interaction between Fe atoms and NH2 groups prevents dopamine molecules from coordinating with the Fe atoms.

Influence of solution treatment on the adsorption and morphology of poly(o-methoxyaniline) layer-by-layer films

It is shown that the adsorption and morphological properties of layer-by-layer films of poly(o-methoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid) (PVS) are affected dramatically by different treatments of the POMA solutions employed to prepare the films. Whereas the dimension of the globular structures seen by atomic force microscopy increases non monotonically during film growth in parent POMA solution, owing to a competition of adsorption/desorption processes, it changes monotonically for the fractionated POMA. The roughness of the latter films depends on the concentration of the solution and saturates at a given size of the scan window. This allowed us to apply scaling laws that indicated a self-affine mechanism for adsorption of the treated POMA.

Morphology characterization of layer-by-layer films from PAH/MA-co-DR13: the role of film thickness

We report on the use of dynamic scale theory and fractal analyses in the Study of distinct growth stages of layer-by-layer (LBL) films of poly(allylamine hydrochloride) (PAH) and a side-chain-substituted azobenzene copolymer (Ma-co-DR13). The LBL films were adsorbed oil glass substrates and characterized with atomic force microscopy with the Ma-co-DR13 at the top layer. The ganular morphology exhibited by the films allowed the observation of the growth process inside and outside the grains. The growth outside the grains was found to follow the Kardar-Parisi-Zhang model, with fractal dimensions of ca. 2.6. One could expect that inside the grains the morphology would be close to a Euclidian surface with fractal dimension of ca. 2 for any growth stage. The latter, however, was observed only for thicker films containing more than 10 bilayers. For thinner films the morphology was well described by a self-affine fractal. Such dependence of the growth behavior with the film thickness is associated with a more complete coverage of adsorption sites in thicker films due to diffusion of polymer molecules. (c) 2004 Elsevier B.V. All rights reserved.

Improvement of the chemical resistance of zirconium fluoride glasses coated with a Tiron (R) modified tin oxide layer prepared by the sol-gel process

In order to improve the chemical resistance of zirconium fluoride glass a protective transparent SnO2 layer was deposited by the solgel dip-coating process in the presence of Tiron (R) as particle surface modifier agent. After water immersion for different periods of time, both coated and non-coated fluoride glasses were analyzed by scanning electron microscopy, mass loss evaluation, infrared spectroscopy and X-ray photoelectron spectroscopy. In contrast to the effects occurring for non-coated glass, where the surface undergoes a rapid selective dissolution of the most soluble species, the results for the SnO2-coated glass showed that the filling of the film nanopores by dissolved glass material results in a hermetic barrier protecting the glass surface. The selective glass dissolution was confirmed by liquid chromatography measurements of the etching solution after each exposure time. (c) 2006 Elsevier B.V. All rights reserved.

Photoinduced phenomena in layer-by-layer films of poly(allylamine hydrochloride) and Brilliant Yellow azodye

The nanoscale interactions between adjacent layers of layer-by-layer (LBL) films from poly(allylamine hydrochloride) (PAH) and azodye Brilliant Yellow (BY) have been investigated, with the films employed for optical storage and the formation of surface-relief gratings. Using Fourier transform infrared spectroscopy, we identified interactions involving SO3- groups from BY and NH3+ groups from PAH. These electrostatic interactions were responsible for the slow kinetics of writing in the optical storage experiments, due to a tendency to hinder photoisomerization and the subsequent reorientation of the azochromophores. The photoinduced birefringence did not saturate after one hour of exposure to the writing laser, whereas in azopolymer films, saturation is normally reached within a few minutes. on the other hand, the presence of such interactions prevented thermal relaxation of the chromophores after the writing laser was switched off, leading to a very stable written pattern. Moreover, the nanoscale interactions promoted mass transport for photoinscription of surface-relief gratings on PAH/BY LBL films, with the azochromophores being able to drag the inert PAH chains when undergoing the trans-cis-trans photoisomerization cycles. A low level of chromophore degradation was involved in the SRG photoinscription, which was confirmed with micro-Raman and fluorescence spectroscopies.

a-b axis-oriented lanthanum doped Bi4Ti3O12 thin films grown on a TiO2 buffer layer

a-b axis-oriented, lanthanum doped Bi4Ti3O12 (BLT) thin films with a TiO2 rutile buffer layer deposited on Pt/Ti/SiO2/Si substrates were grown by the soft chemical method. Butterfly dielectric behavior has been achieved and can be ascribed to the ferroelectric domain switching. The remanent polarization and the coercive voltage for the film deposited on TiO2 buffer layer were 22.2 mu C/cm(2) and 1.8 V, respectively. Random-oriented BLT films showed a reduction in switching polarization when compared to the a-b axis-oriented films. Due to the excellent physical properties, these films are a promising candidate for use in lead-free applications in ferroelectric devices. (c) 2006 American Institute of Physics.

Alumina/zirconia composite coated by biomimetic method

In this study, a bioactive zirconia-toughened alumina (ZTA) composite was developed for orthopedic applications. This composite was obtained by slip casting of suspension powder mixtures.Biomimetic processes were used to grow a bone-like apatite layer on composite substrates using sodium silicate solution as a nucleating agent and simulated body fluids. The composites, with or without coating, were characterized by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and scanning electron microscopy (SEM) with energy dispersion spectroscopy (EDS), and their apparent density was determined by the Archimedes method. The composites obtained by this process possessed the expected stiffness and dimensions and their density values were similar to those of the composite's theoretical density (98.8%TD). The morphology of the hydroxyapatite formed on the composite surface was homogeneous and composed of small globules, characterizing a carbonated hydroxyapatite. The results of the tests indicated that the method employed to produce the composite and its coating was efficient under the conditions of this study. (c) 2006 Elsevier B.V. All rights reserved.

Adsorption processes in layer-by-layer films of poly(o-methoxyaniline): the role of aggregation

In this work we investigate the effect from the solution concentration on aggregation in layer-by-layer (LBL) films of poly(omethoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid). Films are adsorbed on hydrophilized glass substrates and characterized with UV-Vis spectroscopy and atomic force microscopy. The formation of aggregates is favored in more concentrated solutions, leading to an increase in the diameter of the domains. This is caused by stronger polymer-polymer interactions under high concentrations. The size of POMA aggregates in solution is estimated to be larger than in LBL films, which is surprising because one should expect aggregates from solution to coalesce into larger aggregates in the deposited films. This unexpected result may be explained by a swelling effect of aggregates in the aqueous POMA solutions, consistent with other reports in the literature which consider the aggregates in solution to be made up of smaller aggregates. Upon adsorption on a solid substrate to form the LBL film, a molecular reorganization probably takes place, resulting in smaller aggregates. It is also found that the size distribution of the POMA domains in the LBL films is determined by the concentration of the solution. (C) 2002 Elsevier B.V. B.V. All rights reserved.