Publications

Abstract The use of deep eutectic solvents (DES) for metal electrodeposition has become an area of interest in the recent years however the use of additives on the electrodeposition from deep eutectic solvents is still an unexplored area. In this study we describe the influence of the tartrate ion on the deposition mechanism of zinc and on the resultant morphology of the deposits. Electrochemical techniques were used to characterize the deposition process and scanning electron microscopy was used to study the deposit morphology. It is shown that the presence of potassium hydrogen tartrate in ethaline does not alter the generic voltammetric profile of zinc in solution but in contrast the presence of tartaric acid cause major modifications. From the analysis of the chronoamperometric transients a 3D progressive nucleation mechanism is proposed for the deposition of zinc in absence and in the presence of potassium hydrogen tartrate. In the presence of tartaric acid a 2D progressive nucleation mechanism is proposed for the initial part of the deposition then changing to a 3D progressive mechanism. The SEM images reveal that both additives change the morphological characteristics of the deposits. However the use of tartaric acid introduces a more dramatic change.

Abstract Bisnaphthalimidopropyl (BNIP) derivatives have recently been shown to have potential as antileishmanial agents. However, these compounds have some drawbacks, including their low aqueous solubility and some toxic effects. In this study, we designed a drug delivery system for enhanced delivery of BNIP derivative compounds whilst reducing adverse toxic effects, and hence increasing their biological efficacy. A coated drug delivery system based on polymeric nanoparticles of pegylated poly(lactic acid) (PLA), a biodegradable polymer, was successfully achieved. The pegylated PLA nanoformulations loaded with BNIP derivatives were evaluated in an in vitro model of intracellular amastigotes in murine J774 and human THP-1 cells for visceral leishmaniasis using luciferase-expressing Leishmania infantum parasites. Pegylation of PLA nanoparticles significantly reduced the capacity of empty nanoparticles in inhibiting intracellular parasite growth. The BNIP derivatives BNIPDadec and BNIPDaoct exhibited EC50 values (concentration of compound necessary to decrease cell viability to 50% of the untreated control) of ca. 4.5 mu M for THP-1 and J774 cells and ca. 9.0 mu M for mouse bone marrow-derived macrophages. Nanoparticle encapsulation of the BNIP derivative compounds decreased their toxicity towards macrophages by >= 10-fold as evaluated by the MTT assay. The antileishmanial activity of free BNIPDadec was 1.02 +/- 0.41 mu M and 0.73 +/- 0.06 mu M for THP-1 and J774 macrophages, respectively. Pegylation of PLA nanoparticles loaded with BNIPDadec resulted in EC50 values of 1.43 +/- 0.63 mu M and 1.79 +/- 0.77 mu M for THP-1 and J774 macrophages, respectively. A similar trend was observed for free BNIPDaoct and pegylated BNIPDaoct PLA nanoparticles (2.43 perpendicular to 0.19 mu M and 1.23 perpendicular to 0.40 mu M for THP-1 macrophages and 1.36 +/- 0.17 mu M and 1.52 +/- 0.57 mu M for J774 macrophages). The nanoformulations were more efficient in reducing parasitic growth inside human macrophages than in murine cells, suggesting host cell-dependent metabolism.

Abstract Ultraviolet (UV) filters are vital constituents of sunscreens and other personal care products since they absorb, reflect and/or scatter UV radiation, therefore protecting us from the sun's deleterious UV radiation and its effects. However, they suffer degradation, mainly through exposure towards sunlight and from reactions with disinfectant products such as chlorine. On the basis of their increasing production and use, UV filters and their degradation products have already been detected in the aquatic environment, especially in bathing waters. This paper presents a comprehensive review on the work done so far as to identify and determine the by-products of UV filter photodegradation in aqueous solutions and those subsequent to disinfection-induced degradation in chlorinated aqueous solutions, namely swimming pools.

Abstract In this work, the interaction between ethyl(hydroxyethyl) cellulose (EHEC) and three dimeric lysine-based surfactants of distinct chain length (C-6, C-8 and C-10) have been assessed and the system was evaluated in terms of its temperature-dependent gelling capacity. The viscosity profile depends on the specific surfactant, its concentration and temperature. The observed profiles reflected polymer-polymer associations at elevated temperatures and polymer-surfactant interactions, implying the formation of micellartype associations. The systems induce gelation at higher temperatures. Longer chain-length surfactants induce gelation at lower concentrations due to their stronger tendency to selfassemble. The thermo-responsive gels showed gel strength generally lower than 20 Pa.s(n) and a fractal dimension of 2.3-2.4, respectively, indicating the formation of soft gels comprising a tight and homogeneous network. The weakest gel was produced in the presence of the C-6 surfactant. 2D Small-Angle Light Scattering patterns showed a pronounced effect of temperature in terms of the evolution of large hydrophobic clusters, an event precluded when high concentrations of the longer chain surfactants were used.

Abstract We apply a new methodology in the force field generation (Phys. Chem. Chem. Phys. 2011, 13, 7910) to study binary mixtures of five imidazolium-based room-temperature ionic liquids (RTILs) with acetonitrile (ACN). Each RTIL is composed of tetrafluoroborate (BF4) anion and dialkylimidazolium (MMIM) cations. The first alkyl group of MIM is methyl, and the other group is ethyl (EMIM), butyl (BMIM), hexyl (HMIM), octyl (OMIM), and decyl (DMIM). Upon addition of ACN, the ionic conductivity of RTILs increases by more than 50 times. It significantly exceeds an impact of most known solvents. Unexpectedly, long-tailed imidazolium cations demonstrate the sharpest conductivity boost. This finding motivates us to revisit an application of RTIL/ACN binary systems as advanced electrolyte solutions. The conductivity correlates with a composition of ion aggregates simplifying its predictability. Addition of ACN exponentially increases diffusion and decreases viscosity of the RTIL/ACN mixtures. Large amounts of ACN stabilize ion pairs, although they ruin greater ion aggregates.

Abstract In this paper, we apply novel intrinsic analysis methods, coupled with bivariate orientation analysis, to obtain a detailed picture of the molecular-level structure of ionic liquid surfaces. We observe pronounced layering at the interface, alternating non-polar with ionic regions. The outermost regions of the surface are populated by alkyl chains, which are followed by a dense and tightly packed layer formed of oppositely charged ionic moieties. We then systematically change the cation chain length, the anion size, the temperature and the molecular model, to examine the effect of each of these parameters on the interfacial structure. Increasing the cation chain length promotes orientations in which the chain is pointing into the vapor, thus increasing the coverage of the surface with alkyl groups. Larger anions promote a disruption of the dense ionic layer, increasing the orientational freedom of cations and increasing the amount of free space. The temperature had a relatively small effect on the surface structure, while the effect of the choice of molecular model was clearly significant, particularly on the orientational preferences at the interface. Our study demonstrates the usefulness of molecular simulation methods in the design of ionic liquids to suit particular applications.

Abstract A recently described non-viral gene delivery system [dioctadecyldimethylammonium bromide (DODAB)/monoolein (MO)] has been studied in detail to improve knowledge on the interactions between lamellar (DODAB) and non-lamellar-forming (MO) lipids, as a means to enhance their final cell transfection efficiency. Indeed, the morphology, fluidity, and size of these cationic surfactant/neutral lipid mixtures play an important role in the ability of these systems to complex nucleic acids. The different techniques used in this work, namely dynamic light scattering (DLS), fluorescence spectroscopy, differential scanning calorimetry (DSC), cryogenic transmission electron microscopy (cryo-TEM), light microscopy (LM), and surface pressure-area isotherms, allowed fully characterization of the phase behavior and aggregate morphology of DODAB/MO mixtures at different molar ratios. Overall, the results indicate that the final morphology of DODAB/MO aggregates depends on the balance between the tendency of DODAB to form zero-curvature bilayer structures and the propensity of MO to form non-bilayer structures with negative curvature. These results also show that in the MO-rich region, an increase in temperature has a similar effect on aggregate morphology as an increase in MO concentration.

Abstract In the last years, a rising trend of pollen allergies in urban areas has been attributed to atmospheric pollution. In this work, we investigated the effects of SO2 and NO2 on the protein content, allergenicity, and germination rate of Acer negundo pollen. A novel environmental chamber was assembled to exposure pollen samples with SO2 or NO2 at two different levels: just below and two times the atmospheric hour-limit value acceptable for human health protection in Europe. Results showed that protein content was lower in SO2-exposed pollen samples and slightly higher in NO2-exposed pollen compared to the control sample. No different polypeptide profiles were revealed by SDS-PAGE between exposed and nonexposed pollen, but the immunodetection assays indicated higher IgE recognition by all sera of sensitized patients to Acer negundo pollen extracts in all exposed samples in comparison to the nonexposed samples. A decrease in the germination rate of exposed in contrast to nonexposed pollen was verified, which was more pronounced for NO2-exposed samples. Our results indicated that in urban areas, concentrations of SO2 and NO2 below the limits established for human protection can indirectly aggravate pollen allergy on predisposed individuals and affect plant reproduction.

Abstract This is the first report of a computational study of the bioluminescence of ligand-bound Photinus pyralis luciferase. A time-dependent PBEO/molecular mechanics approach was used to study the interaction between excited-state oxyluciferin (Keto-(-1)) and. neighboring active site molecules. The results of these calculations demonstrated that the most important intermolecular interactions are: blue-shifting ionic interactions, red-shifting pi-pi stacking, and red/blue shifting hydrogen bonding. Subsequent molecular dynamics simulations further supported these conclusions.

Abstract Optical steady-state and time-resolved spectroscopic methods were used to study the photoprotolytic reaction of oxyluciferin, the active bioluminescence chromophore of the firefly's luciferase-catalyzed reaction. We found that like D-luciferin, the substrate of the firefly bioluminescence reaction, oxyluciferin is a photoacid with pK(a)* value of similar to 0.5, whereas the excited-state proton transfer (ESPT) rate coefficient is 2.2 x 10(10) s(-1), which is somewhat slower than that of D-luciferin. The kinetic isotope effect (KIE) on the fluorescence decay of oxyluciferin is 2.5 +/- 0.1, the same value as that of D-luciferin. Both chromophores undergo fluorescence quenching in solutions with a pH value below 3.