Publications

Abstract A new methodology for the covalent functionalization of a SAM of 11-amino-1-undecanethiol, previously adsorbed on polycrystalline Au, was successfully applied in order to immobilize a beta-CD layer on surface. A two steps synthetic strategy is proposed based on the activation of the SAM with di-(N-succinimidyl) carbonate for the further inclusion of the beta-CD. The modification of the SAM was followed by PM-FTIRRAS, AFM imaging, CV, and EIS which confirmed the introduction of beta-CD layer. The AFM images allowed the identification of homogeneously distributed beta-CD aggregates over the Au grain microstructure. The electrode was characterized in the presence of electroactive species in solution, with the ability to form inclusion complexes with the beta-CD cavity. Contrary to the reported for other thiolated CD derivative films, the results of this study showed the formation of well-packed and compact structures which strongly reduce non-specific adsorption phenomena. The redox response of the probes at the beta-CD electrode was shown to appear at higher potentials with respect to the response at bare Au. Good correlation was found between the increase of the hydroquinone oxidation peak and, both, the scan rate used in CV experiments (typical behavior of surface-confined species) and the hydroquinone concentration. In the case of dopamine, the processes seem to shifted out of the potential window of SAM stability. The results suggest that this problem could be overcome by improving the design of the device.

Abstract The kinetics and equilibrium of the adsorption of Indanthrene Olive Green (IOG) from aqueous solution onto chitosan have been investigated. The chitosan was characterised in terms of its average degree of de-acetylation (DD) and by XRD, TGA/DTG, IR, SEM and specific BET surface area methods. Batch adsorptions experiments were carried out at different pH values and dye concentrations. It was found that the adsorption process was favoured by acidic pH conditions (4.0-6.0). The adsorption followed second-order rate kinetics and the experimental equilibrium data followed the Langmuir isotherm, thereby suggesting that chemisorption might be the major adsorption mode. Such adsorption also occurred on chitosan fibres, although to a significantly lower extent than on crushed chitosan. The corresponding thermodynamic parameters (ΔG, ΔH and ΔS) were calculated. The positive values obtained for ΔH (161.7 kJ/mol) and ΔS [559.9 J/(mol K)] suggest that the adsorption process was endothermic, with the randomness of the system increasing during the adsorption process. A simplified adsorption model has also been proposed.

Abstract Mixed polymer-surfactant systems have been intensively investigated in the last two decades, with the main focus on surfactant micelles as the surfactant aggregate in interaction. The main types of phase behavior, driving forces and structural/rheological effects at stake are now fairly well understood. Polymer-vesicle systems, on the other hand, have received comparatively less attention from a physico-chemical perspective. In this review, our main goal has been to bridge this gap, taking a broad approach to cover a field that is in clear expansion, in view of its multiple implications for colloid and biological sciences and in applied areas. We start by a general background on amphiphile self-assembly and phase separation phenomena in mixed polymer-surfactant solutions. We then address vesicle formation, properties and stability not only in classic lipids, but also in various other surfactant systems, among which catanionic vesicles are highlighted. Traditionally. lipid and surfactant vesicles have been studied separately, with little cross-information and comparison, giving duplication of physico-chemical interpretations. This situation has changed in more recent times. We then proceed to cover more in-depth the work done on different aspects of the associative behavior between vesicles (of different composition and type of stability) and different types of polymers, including polysaccharides. proteins and DNA. Thus. phase behavior features. effects of vesicle structure and stability, and the forces/mechanisms of vesicle-macromolecule interaction are addressed. Such association may generate gels with interesting theological properties and high potential for applications. Finally, special focus is also given to DNA, a high charge polymer. and its interactions with surfactants, and vesicles. in particular, in the context of gene transfection studies.

Abstract The design of efficient liposomal systems for drug delivery is of considerable biomedical interest. In this context, vesicles prepared from cationic/anionic surfactants may offer several advantages, mainly due to their spontaneity in formation and long-term stability. There is also an impending need to produce less toxic, more biocompatible amphiphiles, while maintaining the desirable aggregation properties. In this work, we present data for acute toxicity to Daphnia magna (IC(50)), and potential ocular irritation (HC(50)) for some newly prepared ionic surfactants with dodecyl chains, derived from the amino acids tyrosine (Tyr), serine (Set), hydroxyproline (Hyp) and lysine (Lys). The micellization behavior of the compounds, evaluated from surface tension measurements, is presented and compared to more conventional ionic amphiphiles. Two types of spontaneouly formed catanionic vesicles, composed either by a dodecyltrimethylammonium bromide (DTAB)/Lys-derivative and or Ser-/Lys-derivative mixture, have also been tested for their ecotoxicity and hemolytic potential. All the micelle-forming surfactants as well as the vesicle-containing mixtures are found to have lower ecotoxicity than the reference surfactant DTAB. Moreover, the results from hemolysis and hemoglobin denaturation tests show that the Tyr- and Lys-derivatives are moderately irritant, whereas the Hyp- and Ser-ones are just slightly irritant. Even more significantly, the vesicle-containing mixtures exhibit lower hemolytic activity than the neat surfactants, a positive result for their potential use in liposomal formulations.

Abstract The extent to which humans and wildlife are exposed to the vast array of anthropogenic chemicals and their degradation products, along with related naturally occurring compounds, is nowadays an important issue. The study of the physical-chemical properties of the compounds and/or degradation products is an important subject because some of them are intrinsically related to its resistance to degradation and/or bioaccumulation. Accordingly, the study of the electrochemical behavior of the selective serotonin reuptake inhibitor fluoxetine and its main metabolite norfluoxetine was investigated. The identification of the oxidation processes was done via two fluoxetine analogues, 1-(benzyloxy)-4-(trifluoromethyl)benzene and N-methyl-3-phenylpropan-1-amine hydrochloride. The oxidative processes occurring in fluoxetine are pH-dependent and were ascribed to the chemical moieties present in the molecule: the secondary amine group and the substituted aromatic nucleus. To perform an unequivocal ascription, the structural preferences of the drug and metabolite were also determined, by Raman spectroscopy coupled to quantum mechanical calculations (at the DFT level). The analytical data obtained in this work will allow the development of a rapid and unequivocal spectroscopic procedure suitable for fluoxetine identification, as well as to distinguish between the drug and its main metabolite.

Abstract The properties of the interface between platinum, gold and glassy carbon electrodes and a deep eutectic ionic liquid based on choline chloride and glycerol were assessed using cyclic voltammetry and electrochemical impedance spectroscopy. The double layer differential capacitance, obtained from electrochemical impedance, reveals a slight dependence of the potential but it is sensitive to the electrode material. In contrast to high temperature inorganic melts the differential capacitance increases with temperature.

Abstract In this work we describe and compare the synthesis of four new hexylamides of hydrocinnamic acids, namely hexylamide of hydrocinnamic, 3,4-dimethoxyhydrocinnamic, 4-hydroxy-3-methoxyhydrocinnamic and 3,4-dihydroxyhydrocinnamic acids via pentafluorophenyl esters (PFPEs) versus pentafluorophenyl thioesters (PFPTs) intermediates. It was found that the PRE are the best intermediates for this kind of synthesis giving reactions with less by products, easier work-up, higher overall yields and with the best reactivity towards hexylamine. The X-ray structures of two PRE are also reported.

Abstract The synthesis of some novel monomeric serine- and tyrosine-based cationic and 4-hydroxyproline-based anionic surfactants, having a long lipophilic alkyl chain directly attached to the nitrogen atom of the amino acid, is described. The most efficient synthetic methodologies were established: reductive amination of the corresponding 'fatty' aldehydes, followed by methylation and deprotection (serine and tyrosine) to obtain the cationic surfactants; or reductive amination followed by saponification (4-hydroxyproline) to obtain the anionic ones. All the compounds were obtained in good to excellent yields. An assessment of their micellization properties and surface activity by tensiometry showed fairly good performance levels.

Abstract A chemical sensor for mercury(II) (Hg(II)) was developed based on the quenching of the fluorescence of cadmium sulfide (CdS) quantum dots (QDs) coated with polypropylenimine tetrahexacontaamine dendrimer ( DAB) generation 5, CdS-DAB nanocomposites. The synthesis and characterization of CdS-DAB nanocomposites by means of EDXA, SEM and steady state luminescence is described. Macroscopic spherical structures are observed by electronic microscopy and the wavelength for the maximum fluorescence emission occurs at 535 nm (excitation at 351 nm). Stern-Volmer plots show a linear response in the range of 1 x 10(-6) to 1 x 10(-5) M with a quenching constant (K(sv)) of 1.5 x 10(5) M(-1). A parallel factor (PARAFAC) analysis model confirmed that Hg( II) alone provokes quenching of the fluorescence. Cu(II) and Pb(II) also quench the fluorescence of CdS-DAB nanocomposites, with a K(sv) = 1.9 x 10(5) M(-1) and K(sv) = 2.2 x 10(-4) M(-1), respectively, and Cd(II), Zn(II), Co(II) and Ni(II) have no effect. Ionic strength, in the range from 1.25 x 10(-3) up to 2 M, provokes a shift in the wavelength of the maximum of the emission spectra, from 482 to 677 nm.

Abstract The conformational behaviour of several biologically relevant hydroxycinnamic systems - ferulic acid and its methyl, ethyl, propyl and butyl esters - was studied by quantum mechanical calculations, at the DFT level. A full geometry optimisation was carried out, as well as a Fourier analysis of the main internal rotations within these molecules. The geometrical preferences of these compounds result from a balance between the stabilising resonance and hydrogen bonding effects and the destabilising non-bonding repulsions, the most stable conformers displaying an s-cis conformation and hydroxyl/methoxyl substituent groups coplanar to the aromatic ring. The results thus obtained allow a better understanding of the well recognised in vitro and in vivo antioxidant and growth-inhibiting properties of this type of phenolic systems. (C) 2009 Published by Elsevier B.V.