Publications

Abstract 4-Methylbenzylidene camphor (4MBC) is an organic UV filter commonly used in sunscreens and many personal care products due to its ability to protect human skin against UVB solar radiation. 4MBC can exist as a (E)- or (Z)-isomer due to an exocyclic carbon-carbon double bond. In sunscreen formulations the (E) isomer predominates but under light exposure isomerization occurs from (E) to (Z). In this study we have performed density functional theory calculations with the B3LYP hybrid functional and two basis sets: 6-31G(d) and 6-311G(d,p) to obtain the gas-phase molecular structure and energetics of the (E)- and (Z)-isomers of 4MBC. For comparison and validation purposes this study has been extended to the parent molecule: camphor. To obtain more accurate energy values we have also used the G3(MP2)//B3LYP method. The standard molar enthalpy of formation of 4MBC in the gas-phase, at T = 298.15 K, was derived from these calculations using appropriately chosen reactions.

Abstract In this study we have performed a density functional theory (DFT) study of the molecular structure and energetics of the enol and keto tautomers of UVA filter 4-tert-butyl-4'-methoxydibenzoylmethane (BMDBM) and for comparison and validation purposes a similar study has been carried out for the parent molecule: dibenzoylmethane (DBM). The molecular structure of the enol and keto tautomers were obtained at the B3LYP/6-311++G(d,p) level. The enol forms were found to have a strong intramolecular resonance assisted hydrogen bond that accounts for the greater energetic stability of the enol relative to the keto form. The aromatic character of the six-membered enol rings has been analyzed by calculation of Nucleus Independent Chemical Shifts (NICS). The standard molar enthalpy of formation in the gas phase of BMDBM was derived from appropriately chosen reactions.

Abstract This is the first theoretical study of the relationship between superoxide anion and firefly chemiluminescence, in DMSO. Electron transfer reactions between luciferin dianionic/carbanionic/radical species and superoxide were studied in order see if an alternative explanation existed for the consumption of the latter species, without correlating it with a role on luciferin chemiluminescence. Despite the finding that luciferin may indeed inhibit the formation of the superoxide anion, no theoretical evidence was found that showed that this molecule is consumed in a non-chemiluminescence reaction. Therefore, it is concluded that the superoxide anion is indeed related to the firefly luciferin chemiluminescence.

Abstract This a theoretical Letter based on density functional theory, on the role of superoxide anion in firefly chemiluminescence in DMSO. We have found that this anion can attack luciferin radical molecules, thus forming a luciferin-like trianion. This latter molecule transfers an oxygen atom, which results in the formation of oxyluciferyl radical dianion and carbon dioxide molecules. Oxyluciferin is finally formed after an electron transfer from oxyluciferyl radical dianion to tert-BuO center dot radical molecules. Thus, we have found evidence that firefly oxyluciferin can be formed in a energetically favorable superoxide anion-assisted reaction, without the need for the formation of firefly dioxetanone.

Abstract The preparation of polymers imprinted with common aromatic solvents such as benzene and toluene is an under-exploited subject of research. The present study was aimed at the understanding of whether true solvent memory effects can be achieved by molecular imprinting, as well as if they are stable at elevated temperature. A set of copolymers, comprising low and high cross-linking levels, was prepared from four different combinations of functional monomer and cross-linker, namely methacrylic acid (MAA)/ethylene glycol dimethacrylate (EGDMA), methyl methacrylate (MMA)/EGDMA, MAA/divinyl benzene (DVB) and MMA/DVB. Each possible combination was prepared separately in benzene, toluene and acetonitrile. The obtained materials were applied as coatings onto nickel-titanium (Ni-Ti) alloy wires which were incorporated into solid-phase microextraction devices and finally tested for their ability to competitively adsorb vapors from the headspace of an aqueous solution containing a few volatile organic compounds. Porosity analysis showed that, regardless of the solvent used, only a high cross-linking level permitted the preparation of mesoporous copolymers (BJH radius typically in the range 13-15 nm), a requirement for providing accessibility to the targeted nanoscale-imprinted cavities. A noticeable exception was, however, observed for the MMA/DVB copolymers which exhibited much diminished BJH radius. The porosity data correlated well with the extraction profiles found, which suggested the presence of benzene-imprinted sites in all the highly cross-linked copolymers prepared in benzene, except for the MMA/DVB copolymers. Concerning the effect of an elevated conditioning temperature on the memoryeffects created by the imprinting process, the results were clearly indicative that the tested copolymers, including the more robust highly cross-linked ones, are not suitable for high temperature applications such as solid-phase microextraction coupled to gas chromatography.

Abstract The behavior of a fluorescent nanocomposite, obtained by means of a thiol polypropylenimine dendrimer of third generation coated with CdSe quantum dots, and embedded in a hydrophilic cellulosic membrane as support is electrochemically studied in order to evaluate its applicability as a sensor in liquid media. The characterization of the nanocomposite by TEM and EDAX shows uniform nano morphology (size comprised in the range 60-90 nm) and composition, respectively. The analysis of the engineered hybrid cellulose-dendrimer quantum dots material by confocal fluorescence microscopy indicates almost mono-dispersion distribution of the nanocomposite when irradiated under UV light, while its presence on the film surface was determined by X-ray photoelectron spectroscopy. Impedance spectroscopy measurements performed with dry membrane samples show a decrease in the conductivity and dielectric constant of the modified membrane in comparison with the raw support. Electrical changes in the modified film associated to the presence of Cd(II) uptakes from a Cl2Cd solution were also obtained. These results support the possible application of this nanocomposite material as heavy metal sensor in liquid media.

Abstract In this work we present a fundamental study of the electrodeposition of tin from Deep Eutectic Solvents (DES) formed by a mixture of choline chloride and different hydrogen bond donors (HBD). Results shows that choline chloride based solvents can be successfully used for the electrodeposition of tin. Furthermore we demonstrate that the choice of hydrogen bond donor does not affect, significantly, the chemistry of tin in solution and we characterize the first stages of tin deposits at glassy-carbon (GC) electrode. The electrochemical characterization of tin deposits is carried out using cyclic voltammetry and chronoamperometry. The comparison of the theoretically and experimentally obtained current transients via dimensionless plots based on Bewick-Fleischman-Thirsk (BFT) theory, Scharifker and Hills (SH) and Scharifker and Mostany (SM) models and a non-linear fitting method showed that tin nucleation on GC surface occurs though a 3D instantaneous process with growth controlled by diffusion.

Abstract Recent years have seen a significant increase in published data supporting the positive effects of statins on neurodegenerative diseases, in particular on Alzheimers disease. Statins show neuroprotective activity by a combination of different cellular and systemic mechanisms that are based on the inhibition of the biosynthesis of cholesterol and isoprenoid by-products. The promising results obtained in vivo and in epidemiological studies are generally not in accordance with those of placebo-controlled randomized clinical trials. Nevertheless, these results make statins valuable assets for disease prevention rather than therapeutic agents for use when disease symptoms are already displayed. Thus, the modulation of midlife cholesterol and/or statin administration prior to the appearance of dementia or cognitive impairment may have a better long-term outcome.