Publications

Abstract The wide ranges of uses for acetophenone make it more available and expected to accumulate in the biosphere, where consequently it can threat ecosystems. To remediate this problem, the use of Solanum nigrum L. plants for the clean-up of acetophenone-contaminated sites was explored. Also, plant root and shoot biometry and metabolism where assayed to better understand the effects of this organic compound and to pinpoint possible metabolic pathways to be targeted for future manipulations for increasing this plant species' remediation efficiency. Although undergoing through some stress, detected by increases in ROS and lipid peroxidation in both organs, plants were able to rapidly eliminate all acetophenone from the nutrient solution after 7 days of exposure, being this compound mainly detoxified at the root level. Additionally, acetophenone lead to a differential metabolic response in roots and shoots, where antioxidant mechanisms where differentially activated, while nitrogen assimilation was repressed in shoots and activated in roots. These results confirm that S. nigrum is a good phytoremediation tool for acetophenone and suggest that enhancing shoot GS activity may provide more nitrogen precursors for the synthesis of thiolated proteins and glutathione to increase tolerance to acetophenone in roots and shoots, respectively.

Abstract The discovery of new chemical entities endowed with potent, selective, and reversible monoamine oxidase B inhibitory activity is a clinically relevant subject. Therefore, a small library of chromone derivatives was synthesized and screened toward human monoamine oxidase isoforms (hMAO-A and hMAO-B). The structure-activity relationships studies strengthen the importance of the amide spacer and the direct linkage of carbonyl group to the γ-pyrone ring, along with the presence of meta and para substituents in the exocyclic ring. The most potent MAO-B inhibitors were N-(3′-chlorophenyl)-4-oxo-4H-chromene-3-carboxamide (20) (IC50 = 403 pM) and N-(3′,4′-dimethylphenyl)-4-oxo-4H-chromene-3-carboxamide (27) (IC50 = 669 pM), acting as competitive and noncompetitive reversible inhibitors, respectively. Computational docking studies provided insights into enzyme-inhibitor interactions and a rationale for the observed selectivity and potency. Compound 27 stands out due to its favorable toxicological profile and physicochemical properties, which pointed toward blood-brain barrier permeability, thus being a valid candidate for subsequent animal studies. © 2016 American Chemical Society.

Abstract An alternative route is proposed for direct electrodeposition of TiO2 films. The electrochemical behaviour of Ti (IV) species in the deep eutectic solvent formed between choline chloride (ChCl) and ethylene glycol (EG) was studied by chronoamperometry and cyclic voltammetry. It was discussed that during the cathodic scan soluble subvalent TiCl chi species were formed using the eutectic system 1ChCl:2EG. Using ethylenediamine or LiF as additives it was possible to obtain a titanium dioxide thin film in the orthorhombic variant named brookite. Chronoamperometric investigations revealed a nucleation mechanism involving the simultaneous presence of 2D instantaneous nucleation process including lattice incorporation and a 3D diffusion-limited nucleation and growth process.

Abstract The thermal and chemical-based methods applied for microbial control in the food industry are not always environmentally friendly and may change the nutritional and organoleptic characteristics of the final products. Moreover, the efficacy of sanitizing agents may be reduced when microbial cells are enclosed in biofilms. The objective of this study was to investigate the effect of photodynamic inactivation, using two xanthene dyes (rose bengal and erythrosine) as photosensitizing agents and green LED as a light source, against Staphylococcus aureus, Listeria innocua, Enterococcus hirae and Escherichia coli in both planktonic and biofilm states. Both photosensitizing agents were able to control planktonic cells of all bacteria tested. The treatments altered the physicochemical properties of cells surface and also induced potassium leakage, indicating damage of cell membranes. Although higher concentrations of the photosensitizing agents (ranging from 0.01 to 50.0 mu mol/L) were needed to be applied, the culturability of biofilm cells was reduced to undetectable levels. This finding was confirmed by the live/dead staining, where propidium iodide-labeled bacteria numbers reached up to 100%. The overall results demonstrated that photoinactivation by rose bengal and erythrosine may be a powerful candidate for the control of planktonic cells and biofilms in the food sector.

Abstract Evolution from fossil fuel energy to renewable energy sources and technologies is in the spotlight towards an accelerated energy transition process. One of the challenges of the intermittent renewable energy production is related to the existence of an appropriate energy storage technology in order to effectively use the renewable energy generated. Electrochemical energy storage devices rely on the key property of the electrical double layer integral capacitance. The use of mixed ionic liquids can be an effective strategy to increase the performance of electric double layer capacitors. Here, the studies on the interfacial behaviour of ionic liquids mixtures containing a common ion for a model mercury/ionic liquid interface are reported. Enhancement of the differential capacitance, nearly 3 times higher compared to ILs in the pure state, was achieved by an appropriate combination of ion size both in cation and the anion and asymmetry. The results are interpreted as a consequence of surface voids occupation and by the accumulation of more counter ions and displacement larger anion by the smaller anion in the mixture.

Abstract The results of experimental (conductometry, NMR-diffusometry) and computational (MD simulations) studies on the binary mixtures of room-temperature imidazolium- and pyridinium-based ionic liquids (RTILs) with acetonitrile (AN), gamma-butyrolactone (gamma-BL) and propylene carbonate (PC) over the wide composition range are presented. The conductometric analysis was carried out in the RTILS mole fraction (chi(RTIL),) range between 0.0 and 0.5 in the temperature ranges from 278.15 to 328.15 K. Notably, all binary systems exhibit conductivity maximum at, chi(RTIL), between 0.1 and 0.2. This maximum slightly shifts towards smaller chi(RTIL), as counter-ion gets larger. Self-diffusion coefficients of solvent molecules and cations were obtained by means of H-1-NMR-diffusometry in mixtures of 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide tetrafluoroborate, trifluoro methanesulfonate and hexafluorophosphate with PC, gamma-BL and AN over the whole concentration range at 300 K. The relative diffusion coefficients of solvent molecules to cations as a function of composition were established to be depended on a solvent but not on the anion of RTIL. In all cases the relative diffusion coefficients demonstrate a plateau at chi(RTIL) < 0.2 and then increase significantly for AN, moderately for gamma-BL or negligibly for PC at higher RTIL content. Such behavior was attributed to the different solvation ability of the investigated solvents. In the mixtures with [BMIM] [PF6] anion diffusion coefficients derived from P-31 NMR were found to be higher than the corresponding values for cation in RTIL-depleted systems and lower in the RTIL-enriched systems. The inversion of relative ion diffusion is observed near the equimolar composition and being insensitive to the solvent. At this point a remarkable change in the diffusion mechanism of ion of RTIL is expected. Additionally, molecular dynamics simulations on the binary mixtures of 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium tetrafluoroborates with AN were performed. The conductivity correlates with a composition of ion aggregates simplifying its predictability. Large amounts of AN stabilize ion pairs, although destroy greater ion aggregates. Based on the simulation results, we show that conductivity of the studied mixtures significantly depend on the ion aggregation.

Abstract In this work, electrically-conducting poly(Toludine Blue) was employed for the first time as synthetic receptor film, prepared by Molecular Imprinting strategies and using electrochemical methods, for the specific screening of breast cancer biomarker Carbohydrate Antigen 15.3 (CA 15-3). The protein imprinted poly(Toluidine Blue) film was grown in a pre-formed Toluidine Blue (TB) tailed SAM at the AuSPE surface, which greatly enhanced the stability against degradation of the Molecular Imprinted Polymer (MIP) film at the electrode surface. The MIP receptor film recognition ability towards the protein was investigated by fitting data to Freundlich isotherm. The binding affinity (K-p) obtained for the MIP system was significantly higher (similar to 12-fold) to that obtained for the NIP system, demonstrating the success of the approach in creating imprinted materials that specifically respond to CA 15-3 protein. The incubation of the MIP modified electrode with increasing concentration of protein (from 0.10 U mL(-1) to 1000 U mL(-1)) resulted in a decrease of the ferro/ferricyanide redox current. The device displayed linear response from 0.10 U mL(-1) to 100 U mL(-1) and LODs below 0.10 U mL(-1) were obtained from calibration curves built in neutral buffer and diluted artificial serum, using DPV technique, enabling the detection of the protein biomarker at clinically relevant levels. The developed MIP biosensor was applied to the determination of CA 15-3 in spiked serum samples with satisfactory results. The developed device provides a new strategy for sensitive, rapid, simple and cost-effective screening of CA 15-3 biomarker. Importantly, the overall approach seems suitable for point-of-care (PoC) use in clinical context.

Abstract Computational modeling is more and more often used in studies of novel ionic liquids. The inevitable side-effect is the growing number of similar computations that require automation. This article introduces NaRIBaS (Nanomaterials and Room Temperature Ionic Liquids in Bulk and Slab)-a scripting framework that combines bash scripts with computational codes to ease modeling of nanomaterials and ionic liquids in bulk and slab. NaRIBaS helps to organize and document all input and output data, thus, improving the reproducibility of computations. Three examples are given to illustrate the NaRIBaS workflows for density functional theory (DFT) calculations of ionic pairs, molecular dynamics (MD) simulations of bulk ionic liquids (ILs), and MD simulations of ILs at an interface.

Abstract Imprinting chondroitin sulfate (CS)/silica composites with Pb(II) and Cu(II) cations was explored with CS of bovine and different fish species origin. The process was based on the assumption that particular arrangements of the linear CS chains in aqueous solution, induced so as to accommodate cross complexation with the cations, would be embodied into a tridimensional matrix created through an organoalkoxysilane sol-gel scheme. The presence of Cu(II) in the synthesis of the composites did not result in the production of significantly stronger Cu(II)-oriented binding arrangements, and therefore, the imprinting was not successful. Inversely, for Pb(II), the materials obtained exhibited a memory effect for the Pb(II) ions, expressed in the observation of stronger (13%-44%) binding as compared to the nonimprinted counterparts, and increased selectivity (1.5-2 folds) against Cd(II). The imprinting features observed were dependent on the CS source. However, it was not possible to identify, among a set of their properties (carboxylate and sulfate abundance, percent of disulfated units, 4S/6S ratio, and molecular weight), any that correlated directly with the observed imprinting features. The augmented selectivity provided by the cation-imprinting process may be advantageous in areas such as analytical separation, remediation, purification, sensing, and others, particularly in those cases where a certain cation is of special interest within a mixture of them.

Abstract Despite research efforts to discover new drugs for Parkinson treatment, the majority of candidates fail in preclinical and clinical trials due to inadequate pharmacokinetic properties, namely blood-brain barrier permeability. Within the high demand to introduce new drugs to market, nano technology can be used as a solution. Accordingly, PEGylated PLGA nano particles (NPs) were used as a smart delivery carrier to solve the suboptimal aqueous solubility, which precludes its use in in vivo assays, of a potent, reversible, and selective monoamine oxidase B inhibitor (IMAO-B) (coumarin C75, IC50 = 28.89 +/- 1.18 nM). Long-term stable PLGA@C75 NPs were obtained by nanoprecipitation method, with sizes around 105 nm and a zeta potential of -10.1 mV. The encapsulation efficacy was around 50%, achieving the final C75 concentration of 807 +/- 30 mu M in the nano formulation, which corresponds to a therapeutic concentration 27828-fold higher than its IC50 value. Coumarin C75 showed cytotoxic effects at 50 mu M after 48 and 72 h of exposure in SH-SY5Y, Caco-2, and hCMEC/D3 cell lines. Remarkably, no cytotoxic effects were observed after nanoencapsulation. Furthermore, the data obtained from the P-gp-Glo assay and the cellular uptake studies showed that C75 is a P-glycoprotein (P-gp) substrate having a lower uptake profile in intestinal and brain endothelial cells. Moreover, it was shown that this membrane transporter influences C75 permeability profile in Caco-2 and hCMEC/D3 cells. Interestingly, PLGA NPs inhibited P-gp and were able to cross intestinal and brain membranes allowing the successful transport of C75 through this type of biological barriers. Overall, this work showed that nanotechnology can be used to solve drug discovery related drawbacks.