Publications

Abstract Based on the strong interaction of noble metal particles with the sulphur atoms of thiophene derivatives, platinum nanoparticles (Pt-NPs)-dispersed poly(3-methylthiophene) (P{3-MeTh}) thin films have been successfully prepared. Evidence of the Pt-NPs confinement in the polymer was provided by the electrocatalytic activity of the modified electrodes towards the dissolved oxygen reduction reaction. The efficient immobilization by self-assembly of thiolated oligonucleotides on the embedded Pt-NPs could be monitored by electrochemical quartz crystal microbalance (EQCM) as well as the subsequent hybridization with the complementary sequence. The good conducting properties and high surface area of P(3-MeTh)/Pt-NPs modified electrodes also allowed the detection of both processes by cyclic voltammetry.

Abstract This paper describes a simple apparatus we have developed for determining elastic properties of materials. The easily constructed system may be used to measure the elongation or compression of a sample to which a succession of loads is applied. This allows stress-strain curves to be plotted and analyzed. We describe the construction and use of the apparatus and present some sample data. © 2011 American Association of Physics Teachers.

Abstract Taking advantage of the spontaneous deposition of noble metals on polymers containing sulphur, the inclusion of gold and platinum in poly(3-methylthiophene) and poly(3,4-ehylenedioxythiophene) (PEDOTh) layers, achieved by immersion of the polymer into the metal nanoparticles suspension, is reported in the present work. Platinum and gold nanoparticles (NPs), with diameters between 3 and 17 nm, have been prepared from colloidal methods (citrate or borohydride reduction in the presence of citrate capping agent) and characterized by transmission electron microscopy, ultraviolet-visible spectrophotometry and X-ray diffraction (XRD). The electropolymerization was carried out under potentiostatic and potentiodynamic conditions, imparting distinct morphologies, as revealed by atomic force microscopy. After polymer films immersion in the colloidal solutions, evidence of the NPs confinement and distribution was provided by XRD analysis and scanning electron microscopy. For thin layers, the quantity of attached metal NPs could be estimated from quartz crystal microbalance data collected throughout the films immersion. The influence of the polymer type and morphology, NPs nature, size and incorporated amount on the electrocatalytic activity of the so-prepared modified electrodes towards the hydrazine oxidation, in phosphate buffer solution, has been investigated by cyclic voltammetry. The results clearly show the superior properties of potentiodynamically prepared PEDOTh films attaching very small (3 nm) freshly prepared Pt-NPs.

Abstract The preparation of gold nanoparticles (Au-NPs) displaying specific shape, size and surface crystallographic domains has been investigated aiming to clarify the effect of the surface crystallographic orientation, of the synthesised nanoparticles, and surfactant influence on the electrochemical response of the ITO/Au-NPs modified electrodes. Polymorphic and nanorod-shaped Au-NPs have been obtained using distinct synthetic procedures in the presence of cetyltrimethylammonium bromide (CTAB), through seed-mediated growth methods, displaying distinct surface crystallographic domains confirmed by transmission electron microscopy, X-ray diffraction analysis and under potential deposition (UPD) of lead. The nanoparticles have been physically immobilised by casting on indium tin oxide (ITO) surfaces and the electrocatalytic activity of the Au-NPs evaluated using the ascorbic acid (AA) oxidation reaction, by cyclic voltammetry. The polymorphic and distinct surface crystallographic orientations of the Au-NPs were reflected in an irreproducible electrochemical response. Using gold nanorods comprising (1 1 1) and (1 1 0) facets and gold nanocubes consisting of faces displaying (1 0 0) surface domains, by contrasting the behaviour of CTAB-stabilised and clean particles, it has been possible to verify that the distinct voltammetric results are due to the exposure of specific crystallographic orientations owing to dissimilar interaction strength of CAB with those facets.

Abstract This work presents a system for on-line study purposes and for demonstrative operation of water quality monitoring based on previous full-scale trials in a commercial aquaculture facility under the scope of a R&D project. This system is still under development, and was designed for sharing resources in R&D activities and later in distance learning blended courses. An application developed in Lab-VIEW is responsible for receiving information from physical and chemical data (water level, flow, oxygen, temperature, pH, ORP and CO2) through a hardware interface. The acquired data are recorded in a Microsoft Access database that can be locally queried as desired. An IP camera allows students to observe the system in real-time. Students can log into the system and follow the real-time variations of a specific water quality parameter and the synergetic effects of these changes on the levels of other constituents. The water tanks contain no living beings in order to allow free adjustments of the parameters under study. The system description, data and remote access link is integrated in a basic course available in a Moodle® server. The goal of this course is to provide a stimulating interdisciplinary environment to a diverse group of undergraduate students, where critical research questions related to water are addressed. This system, unique in the area concerning with our knowledge, intends to contribute also to students' training on data monitoring and analysis; and to nourish analytical skills and creativity of future scientists by encouraging potential graduate students to go further. Finally, this system allows the students to be familiar with the use of some new information technologies.

Abstract Information on commercial aquaculture systems bacterial communities is scarce. The present study was performed in a turbot shallow raceway recirculating aquaculture system throughout 221 days after initial fish stocking. The dynamics of bacteria attached to a Moving Bed Biofilm Reactor and the distribution of the system culturable planktonic heterotrophic bacteria were assessed. Different levels of free heterotrophic bacteria were found over time: <= 2.6 x 10(4) CFU mL(-1) in incoming and ozonated water and >= 1.5 x 10(6) CFU mL(-1) in raceway and biofilter water. 16S rRNA gene sequencing of nine strains persistently isolated from the system affiliated with Bacteroidetes, alpha-Proteobacteria or gamma-Proteobacteria. Polymerase chain reaction-denaturating gradient gel electrophoresis (PCR-DGGE) data showed temporal and spatial segregation of attached biofilter community. The first 32 days were the most important for bacterial establishment with higher culturable bacteria biomass loadings and higher community diversity. Multivariate canonical correspondence analysis of PCR-DGGE showed that the most common aquaculture water quality descriptors explained 70% of the DGGE pattern variability.

Abstract In spite of recent advances towards understanding the mechanism of firefly bioluminescence, there is no consensus about which oxyluciferin (OxyLH(2)) species are the red and yellow-green emitters. The crystal structure of Luciola cruciata luciferase (LcLuc) revealed different conformations for the various steps of the bioluminescence reaction, with different degrees of polarity and rigidity of the active-site microenvironment. In this study, these different conformations of luciferase (Luc) are simulated and their effects on the different chemical equilibria of OxyLH(2) are investigated as a function of pH by means of density functional theory with the PBE0 functional. In particular, the thermodynamic properties and the absorption spectra of each species, as well as their relative stabilities in the ground and excited states, were computed in the different conformations of Luc. From the calculations it is possible to derive the acid dissociation and tautomeric constants, and the corresponding distribution diagrams. It is observed that the anionic keto form of OxyLH(2) is both the red and the yellow-green emitter. Consequently, the effect of Luc conformations on the structural and electronic properties of the Keto-(-1) form are studied. Finally, insights into the Luc-catalyzed light-emitting reaction are derived from the calculations. The multicolor bioluminescence can be explained by interactions of the emitter with active-site molecules, the effects of which on light emission are modulated by the internal dielectric constant of the different conformations. These interactions can suffer also from rearrangement due to entry of external solvent and changes in the protonation state of some amino acid residues and adenosine monophosphate (AMP).

Abstract Firefly luciferase exhibits a color-tuning mechanism based on pH-induced changes in the structure of the active site. These changes increase the polarity of the active site, and thus modulate the intermolecular interactions between the light emitter and active site molecules. In this study, the effects exerted by adenosine monophosphate (AMP), water molecules, and amino acids of Luciola cruciata luciferase active site on the emission wavelength of oxyluciferin were assessed by TD-DFT calculations. The redshift results mainly from decreased interaction of oxyluciferin with AMP and increased interaction of the emitter with a water molecule and Phe249. Breaking of a hydrogen bond between the benzothiazole oxygen atom with formation of a similar bond to the thiazolone oxygen atom is also instrumental.

Abstract Gold nanowire networks (AuNWNs) with average widths of 17.74 nm (AuNWN1) or 23.54 nm (AuNWN2) were synthesized by direct reduction of HAuCl4 with sodium borohydride powder in deep eutectic solvents, such as ethaline or reline, at 40 degrees C. Their width and length were dependent on the type of solvent and the NaBH4/HAuCl4 molar ratio (32 in ethaline and 5.2 in reline). High resolution transmission electron microscopy (HR-TEM) analysis of the gold nanowire networks showed clear lattice fringes of polycrystalline nanopowder of d = 2.36, 2.04, 1.44, and 1.23 angstrom corresponding to the (111), (200), (220), or (311) crystallographic planes of face centered cubic gold. The purified AuNWNs were used as catalysts for the chemical reduction of p-nitroaniline to diaminophenylene with sodium borohydride in aqueous solution. The reaction was monitored in real time by UV-vis spectroscopy. The results show that the reduction process is six times faster in the presence of gold nanowire networks stabilized by urea from the reline (AuNWN2) than in the presence of gold nanowire networks stabilized by ethylene glycol from ethaline (AuNWN1). This is due to a higher number of corners and edges on the gold nanowires synthesized in reline than on those synthesized in ethaline as proven by X-ray diffraction (XRD) patterns recorded for both types of gold nanowire networks. Nevertheless, both types of nanomaterials determined short times of reaction and high conversion of p-nitroaniline to diaminophenylene. These gold nanomaterials represent a new addition to a new generation of catalysts: gold based catalysts.

Abstract A series of molecular dynamics (MD) simulations of different pregelification mixtures representing intermediate stages of the sol gel process were set up to gain insight into the molecular imprinting process in xerogels, namely, to assess the template gel affinity and template self-aggregation. The physical plausibility of the parametrization was checked, confirming the reliability of the simulations. The simulated mixtures differed in the water/methanol ratio (1:3, 5:3, and 5:1) and in the absence/presence of an organic functional group (phenylaminopropyl-) in the silicate species. The simulation results, expressed mainly by the radial distribution functions and respective coordination numbers, showed that the affinity of the template molecule, damascenone (a hydrophobic species), for the gel backbone would not be attained without the tested functional group, phenylaminopropyl-. The affinity, related to the capability to trap the template within the gel network, was derived mostly from the hydrophobic interaction. It was also inferred from MD simulations that lower water contents (methanol-richer mixtures) would facilitate a better dispersion of both the functional group and the template within the final gel, therefore favoring the imprinting process. From the experimental counterparts of the simulated mixtures, a series of imprinted and nonimprinted xerogels were obtained. There was only one xerogel exhibiting the imprinting effect, namely, the one containing the organic group obtained at the lower water/methanol ratio (1:3), in agreement with predictions from the MD simulations. Such congruence demonstrates the ability of MD simulations to provide information regarding the fine aspects of molecular interactions in pregelification mixtures for imprinting.