Publications

Abstract The standard (p degrees = 0.1 MPa) molar energies of combustion in oxygen at T = 298.15 K of 5-hydroxy- and 6-hydroxy-alpha-tetralone were measured by static bomb calorimetry. The values of the standard molar enthalpies of sublimation at T = 298.15 K were obtained by Calvet microcalorimetry. Combining these results, the standard molar enthalpies of formation of the compounds in the gas-phase at T = 298.15 K have been calculated: 5-hydroxy-alpha-tetralone -(262.5 +/- 2.3) kJ.mol(-1) and 6-hydroxy-alpha-tetralone -(268.1 +/- 2.2) kJ.mol(-1). Additionally, high-level single-point calculations based on density functional theory with the B3LYP hybrid exchange-correlation energy functional and extended basis sets as well as on two more accurate correlated computational techniques of the MCCM/3 suite have been performed for the studied compounds. The agreement between experiment and theory gives us confidence to estimate the enthalpies of formation of 7-hydroxy and 8-hydroxy-alpha-tetralone. Similar calculations were done for 5-, 6, 7-, and 8-hydroxy-beta-tetralone, for which experimental work was not done.

Abstract The standard (p degrees = 0.1 MPa) molar energies of combustion in oxygen, at T = 298.15 K, of solid 3,3-tetramethyleneglutaric acid and the related 3,3-tetramethyleneglutaric anhydride and 3,3-tetramethylenegiutarimide were measured by static bomb combustion calorimetry. The values of the standard molar enthalpies of sublimation, at T = 298.15 K, were obtained by Calvet microcalorimetry, allowing the calculation of the standard molar enthalpies of formation of the compounds, in the gaseous state, at T = 298.15 K. The geometries of the experimentally studied compounds were fully optimized using density functional theory with the B3LYP functional and extended basis sets. More accurate energies were also obtained from single-point calculations at the most stable B3LYP/6-311G** geometries, using the cc-pVTZ basis set. From these calculations the standard molar enthalpies of formation of 3,3-tetramethyleneglutaric acid, 3,3-tetramethyleneglutaric anhydride, and 3,3-tetramethyleneglutarimide were estimated using isodesmic reactions involving glutaric acid, glutaric anhydride, and glutarimide, respectively. Experimental and computational results were used in the discussion of the interrelation of energetics and structure in these compounds and compared with other structurally related compounds.

Abstract Nanocomposite films comprising walled carbon nanotubes (MWCNTs) embedded within poly [Ni(3-Mesalophen-b15-c5)] were deposited on Pt and ITO electrode surfaces by the potentiodynamic polyrnerisation of [Ni(3-Mesalophen-b15-c5)] from solutions containing dispersed MWCNTs. Composites incorporating carbon nanotubes subject to a range of oxidising pre-treatments were compared with those incorporating untreated carbon nanotubes and with the pure polymer. In both cases the use CH3CN and CH2Cl2 as fabrication and characterization media were explored. Films were characterized by voltammetry. electrochemical impedance spectroscopy and scanning electron microscope (SEM). The coating of the carbon nanotubes with polymer varied significantly with pre-treatment and solvent medium; this influenced the final composite morphology and electrical properties. Performance enhancement of the polymer component by the presence of the carbon nanotubes was manifested through the ability to store charge and the ease with which this Could he accomplished; these were parameterized via increased redox capacitance and decreased charge-transfer resistance, respectively. Correlation of impedance parameters with SEM images provided a morphological rationale for composite electrical properties.

Abstract The mechanisms by which methamphetamine (METH) causes neurotoxicity are not well understood. Recent studies have suggested that METH-induced neuropathology may result from a multicellular response in which glial cells play a prominent role, and so it is plausible to suggest that cytokines may participate in the toxic effects of METH. Therefore, in the present work we evaluated the effect of an acute administration of METH (30 mg/kg in a single intraperitoneal injection) on the interleukin (IL)-1 beta, IL-6, and tumor necrosis factor (TNF)-alpha mRNA expression levels in the hippocampus, frontal cortex, and striatum of mice. We observed that METH did not induce changes in the IL-1 beta mRNA expression levels in both hippocampus and striatum, with immeasurable levels in the frontal cortex. Regarding IL-6, METH induced an increase in the expression levels of this cytokine in the hippocampus and striatum, 1 h and 30 min post injection, respectively. In the frontal cortex, the increase in IL-6 mRNA levels was more significant and remained high even after 2 h. Moreover, the expression levels of TNF-alpha were increased in both hippocampus and frontal cortex 30 min post METH administration, with immeasurable levels in the striatum. We conclude that the pro-inflammatory cytokines IL-6 and TNF-alpha rapidly increase after METH administration, providing a new insight for understanding the effect of this drug of abuse in the brain.

Abstract The desorption of a self-assembled monolayer (SAM) of 11-amino-1-undecanethiol (AUT) formed on an Au polycrystalline electrode was investigated with the purpose of establishing the most efficient method for SAM removal prior to electrode re-Use. The cleanliness of the surface was evaluated by assessing the characteristics (and their reproducibility) of a newly prepared SAM (on a freshly cleaned electrode) in the presence of Ru(NH3)(6)(3+/2+) probe species. The simple flame annealing of the modified electrodes showed poor reproducibility. Later, cleaning treatments based on previous reports about the electrochemical desorption of SAMs, were investigated in NaOH, HClO4, and KCl solutions. The anodic removal in alkaline and chloride solutions was not efficient enough due to the effect of the Au surface oxidation and dissolution. The commonly used reductive desorption in alkaline solution did also not offer a high efficiency (in contrast with the behavior described in those reports) probably due to the low stability of the thiolate molecules at high-pH values. In addition, such procedures did not provide a way to visualize the evolution of the process. The oxidative desorption in perchloric acid showed a higher efficiency at each single desorption cycle, and allowed to monitor the extension of the removal by comparing the cyclic voltammograms obtained in that medium with the expected fingerprint for the bare Au. However the voltammetric characterization of new AUT films, prepared on such electrochemically treated surfaces by re-incubation in the AUT solution, showed that the conditions of substrate cleanliness and smoothness necessaries to reproduce a close-packed and compact AUT monolayer were not reached. A new cleaning strategy based on the coupled use of oxidative removal in HClO4 0.1 M and flame annealing showed to be efficient and reproducible, providing the proper substrate precursors for the formation of highly ordered AUT films. The results also showed that the methodology works well in the removal of other SAMs like the one formed by the neutral 1-dodecanethiol (1-DT).

Abstract Surgical adhesives consist on an attractive alternative to suturing or stapling since they can accomplish other tasks, such as haemostasis and the ability to seal air leakages. The application of adhesives would also reduce the surgeries procedure time since they represent an easier and faster method to establish tissue adhesion. The aim of this work was the development of a biodegradable urethane pre-polymer that presents the capacity of reacting with the amino groups present in the biological molecules. Urethanes based on polycaprolactone diol (PCL) were synthesized by reaction of the molecule either with isophorone diisocyanate (IPD-isocyanate) or hexamethylene diisocyanate (HDI-isocyanate). The characterization of the materials was accomplished by: ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared), determination of swelling capacity, stability of NCO groups in the presence of humidity conditions, reaction with aminated substrates (as a simulation of the living tissues) and determination of surface energy by contact angle measurement. The haemocompatibility of the PU was also evaluated by thrombosis and haemolysis tests.

Abstract Impedance spectra (50 kHz-1 Hz) were acquired and used to obtain the differential capacitance at the interfaces between 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6] ionic liquid and three different electrode materials (Hg, Pt, and glassy carbon (GC)) as a function of the applied potential. The electrocapillary curve for the Hg/[BMIM][PF6] interface was obtained from drop time measurements, from which the potential of zero charge was calculated to be -0.39 V (Ag wire). The potential of zero charge is 0.30 V less negative than the potential of differential capacitance minimum. This disagreement suggests that the differential capacitance minimum is not related to a classical diffuse layer minimum. Additional support to this conclusion was obtained from positive temperature coefficient for the differential capacitance in contrast to the negative temperature predicted by the classic Gouy-Chapman model. The results do not support the recent model predictions of bell shaped capacitance curves for room temperature ionic liquids, RTILs.

Abstract Mixtures of cationic and anionic surfactants (catanionic mixtures) are often highly non-ideal, exhibiting strong synergism in their interfacial properties, manifested for instance in significant reduction of the mixture critical micelle concentration (cmc) and enhanced adsorption onto surfaces. The magnitude of such effects is of fundamental interest and has important application-related uses (e.g. in detergent formulation). In this work, the micellization process of mixtures of cationic gemini surfactants of the alkanediyl-alpha,omega-bis (alkyl dimethylammonium bromide) type, denoted by 12-n-12 (where it is the spacer length), with several common anionic surfactants has been investigated by electric conductivity. For the purpose of comparison. cationic-cationic mixtures, where dodecyltrimethylammonium bromide is the second cationic surfactant, have also been investigated. The cationic/anionic mixtures show relatively significant deviations from ideal behavior, depending on the structure of the gemini surfactant and the anionic surfactant. The interaction parameter beta(12), within Rubingh's non-ideal model for mixed micelles, has been calculated for each mixture, as well as the mixed micelle composition as a function of mixture composition. The observed synergism in the different mixtures is interpreted in terms of the molecular structure of the surfactants and corresponding head-head and chain-chain interactions.

Abstract The development of the complex network graphs permits us to describe any real system such as social, neural, computer or genetic networks by transforming real properties in topological indices (TIs). This work uses Randic's star networks in order to convert the protein primary structure data in specific topological indices that are used to construct a natural/random protein classification model. The set of natural proteins contains 1046 protein chains selected from the pre-compiled CulledPDB list from PISCES Dunbrack's Web Lab. This set is characterized by a protein homology of 20%, a structure resolution of 1.6 angstrom and R-factor lower than 25%. The set of random amino acid chains contains 1046 sequences which were generated by Python script according to the same type of residues and average chain length found in the natural set. A new Sequence to Star Networks (S2SNet) wxPython GUI application (with a Graphviz graphics back-end) was designed by our group in order to transform any character sequence in the following star network topological indices: Shannon entropy of Markov matrices, trace of connectivity matrices, Harary number, Wiener index, Gutman index, Schultz index, Moreau-Broto indices, Balaban distance connectivity index, Kier-Hall connectivity indices and Randic connectivity index. The model was constructed with the General Discriminant Analysis methods from STATISTICA package and gave training/predicting set accuracies of 90.77% for the forward stepwise model type. In conclusion, this study extends for the first time the classical TIs to protein star network TIs by proposing a model that can predict if a protein/fragment of protein is natural or random using only the amino acid sequence data. This classification can be used in the studies of the protein functions by changing some fragments with random amino acid sequences or to detect the fake amino acid sequences or the errors in proteins. These results promote the use of the S2SNet application not only for protein structure analysis but also for mass spectroscopy, clinical proteomics and imaging, or DNA/RNA structure analysis.