Development of new decorative coatings based on gold nanoparticles dispersed in an amorphous TiO2 dielectric matrix

The present work is devoted to the optical properties of Au:TiO2 thin films in order to clarify the role of the Au clusters inclusions in the TiO2 dielectric matrix. Three series of films containing about 30 at.% (29.2), 20 at. % (19.8) and 10 at.% (9.3) Au were deposited by dc reactive magnetron sputtering. On thermal annealing in the range from 300 to 800 °C in protective atmosphere, significant changes on the crystalline phases and clusters dimensions were detected. The most promising optical behavior was found for the film 20% Au:TiO2, where the films revealed some colour changes, evolving from several shades of grey to different tones of red. This change in the optical behaviour of the films was found to be correlated with a cluster size increase from 2 to 17 nm. For higher size values (>20 nm) the films, independently of the Au content, showed a golden appearance colour. The optical changes were confirmed by reflectivity and CIELab colour measurements. Regarding the films with 10 and 30 at.% Au, the results confirmed that there is an evident range of compositions and clusters size where the SPR is more evident. Sample A (10 at.% Au) it seems to be in the lower limit of the SPR showing a typical interferometric behavior on the reflectivity measurements, similar to the TiO2 optical behavior. Regarding the 30 at.% Au one, the results seems to indicate that the amount of gold particles and their grain size is in the upper limit to show a SPR activity.Fundação para a Ciência e Tecnologia (FCT) - PTDC/CTM/70037/200

Tailoring the Transport Properties of Mesoporous Doped Cerium Oxide for Energy Applications

Hard-template nanocasted mesoporous cerium oxide possesses a unique combination of thermal stability, high surface area, and short diffusion lengths for mass and gas transport, which makes it relevant for high-temperature catalysis, sensing, and electrochemical applications. Here, we present an in-depth study of a number of mesoporous doped ceria systems, and we assess their fundamental structure and functionalities by complementary transmission electron microscopy imaging and spectroscopy, electron tomography reconstructions, and electrochemical impedance spectroscopy. We employed surface chemical modifications for increasing the ionic conductivity of as-synthesized mesoporous Gd-doped ceria by 2 orders of magnitude, enabling the ionic pathway across mesoporous particles. Complementary bulk doping strategies (by the addition of Pr) result in the easy tuning of the electrical transport mechanisms converting pure ionic mesoporous ceria into a mixed ionic-electronic conductor. The results obtained here are rationalized in light of local charge accumulation and mobility effects, providing a potential tool for engineering transport properties in nanocasted ceria and similar nanostructured materials for use in energy applications in the form of functional composites, infiltrated structures, or catalytic layers

Protective Ag :TiO2 thin films for pressure sensors in orthopedic prosthesis: the importance of composition, structural and morphological features on the biological response of the coatings

DC reactive magnetron sputtered Ag:TiO2 nanocomposite thin films were developed to be used as protective coatings in pressure sensor devices. The coatings, with Ag content varying from 0 to about 30 at.%, were prepared and characterized in order to study their biological response. The as-deposited samples were annealed in vacuum at 500 °C in order to evaluate the influence of their morphological and structural differences over the response elicited upon contact with simulated bodily fluids and cultured human cells, as well as selected microorganisms. The results showed that the annealing treatment produced less porous films with an enhanced structure, with a significant reduction in structural defects and improved crystallinity. Additionally, samples with higher Ag contents (≥12.8 at.%) exhibited Ag agglomerates/clusters at the surface, a result anticipated from the XRD data. The crystallization of the TiO2 matrix was also observed by XRD analysis, albeit delayed by the dispersion of Ag into the matrix. Biological characterization showed that the antimicrobial activity and cytotoxicity of the coatings were directly related with their composition, closely followed by the particular structural and morphological features, namely those resulting from annealing process.This research is partially sponsored by FEDER funds through the program COMPETE—Programa Operacional Factores de Competitividade and by national funds through FCT—Fundação para a Ciência e a Tecnologia, under the projects PEst-C/EME/UI0285/2011, PTDC/SAU-ENB/116850/2010, PTDC/CTM-NAN/112574/2009P. T Matamá acknowledges FCT for Grant SFRH/BPD/47555/2008

Thin films composed of Ag nanoclusters dispersed in TiO2: Influence of composition and thermal annealing on the microstructure and physical responses

Noble metal powders containing gold and silver have been used for many centuries, providing different colours in the windows of the medieval cathedrals and in ancient Roman glasses. Nowadays, the interest in nanocomposite materials containing noble nanoparticles embedded in dielectric matrices is related with their potential use for a wide range of advanced technological applications. They have been proposed for environmental and biological sensing, tailoring colour of functional coatings, or for surface enhanced Raman spectroscopy. Most of these applications rely on the so-called localised surface plasmon resonance absorption, which is governed by the type of the noble metal nanoparticles, their distribution, size and shape and as well as of the dielectric characteristics of the host matrix. The aim of this work is to study the influence of the composition and thermal annealing on the morphological and structural changes of thin films composed of Ag metal clusters embedded in a dielectric TiO2 matrix. Since changes in size, shape and distribution of the clusters are fundamental parameters for tailoring the properties of plasmonic materials, a set of films with different Ag concentrations was prepared. The optical properties and the thermal behaviour of the films were correlated with the structural and morphological changes promoted by annealing. The films were deposited by DC magnetron sputtering and in order to promote the clustering of the Ag nanoparticles the as-deposited samples were subjected to an in-air annealing protocol. It was demonstrated that the clustering of metallic Ag affects the optical response spectrum and the thermal behaviour of the films.This research was sponsored by FEDER funds through the COMPETE program (Programa Operacional Factores de Competitividade) and by FCT (Fundação para a Ciência e a Tecnologia), under the projects PEST-C/FIS/UI607/2013 and PEst-C/EME/UI0285/2013. The authors also acknowledge the financial support by the project Nano4color – Design and develop a new generation of color PVD coatings for decorative applications (FP7 EC R4SME Project No. 315286). J. Borges also acknowledges the support by the European social fund within the framework of realising the project “Support of inter-sectoral mobility and quality enhancement of research teams at Czech Technical University in Prague”, CZ.1.07/2.3.00/30.0034. C. Lopes acknowledges FCT for the PhD grant SFRH/BD/103373/2014. F.M. Couto acknowledges CAPES – Foundation, Ministry of Education of Brazil, Brasília – DF 70040-20, Brazil, funding by stage sandwich doctorate, through PDSE – Doctoral Program Sandwich

Structural and optical properties of Ag: TiO2 nanocomposite films prepared by magnetron sputtering

Three sets of nanocomposite films consisting of different atomic concentrations of Ag dispersed in a TiO2 dielectric matrix were deposited by DC reactive magnetron sputtering, and subjected to several thermal annealing experiments in vacuum, for temperatures ranging from 200 to 600 ºC. The main goal of the present study is to analyse the optical properties of the as-deposited and annealed films in order to clarify the role of Ag inclusions in the TiO2 dielectric matrix. The influence of the thermal annealing in the structural and morphological evolution was then correlated with the changes in the optical behavior of the samples. Significant structural and morphological changes were observed, consisting on the crystallization of Ag and their clustering. Clusters growth as a function of temperature was also observed by the evolution of the diffractograms with the temperature increase. The present study allowed to conclude that at certain concentrations (close to 10 at. %), the films revealed some important changes on the optical properties, commonly known as Surface Plasmon Resonance, SPR. This change in the optical behavior of the films was found to be in accordance with the clusters growth as concluded from the evolution of the diffraction patterns. The optical changes, and the correspondent Surface Plasmon Resonance effect were confirmed by reflectivity and CIELab colour measurements. The samples with lower Ag content (11 at. % and 7 at. %) show typical interferometric behavior on the reflectivity curves, similar to those of “pure” TiO2 samples. After a minimum of reflectance at 300 nm, there was an increase of the reflectivity at higher wavelengths. For the samples annealed between 400 and 600 °C, a red-shift centered at around 500-550 nm is visible in the absorbance spectrum.Fundação para a Ciência e a Tecnologia (FCT) - PTDC/CTM/ 70037/2006

A Pilot Study for Metabolic Profiling of Obesity-Associated Microbial Gut Dysbiosis in Male Wistar Rats

Obesity is one of the most incident and concerning disease worldwide. Definite strategies to prevent obesity and related complications remain elusive. Among the risk factors of the onset of obesity, gut microbiota might play an important role in the pathogenesis of the disease, and it has received extensive attention because it affects the host metabolism. In this study, we aimed to define a metabolic profile of the segregated obesity-associated gut dysbiosis risk factor. The study of the metabolome, in an obesity-associated gut dysbiosis model, provides a relevant way for the discrimination on the different biomarkers in the obesity onset. Thus, we developed a model of this obesity risk factors through the transference of gut microbiota from obese to non-obese male Wistar rats and performed a subsequent metabolic analysis in the receptor rats. Our results showed alterations in the lipid metabolism in plasma and in the phenylalanine metabolism in urine. In consequence, we have identified metabolic changes characterized by: (1) an increase in DG:34:2 in plasma, a decrease in hippurate, (2) an increase in 3-HPPA, and (3) an increase in o-coumaric acid. Hereby, we propose these metabolites as a metabolic profile associated to a segregated dysbiosis state related to obesity disease