Publications

Abstract In this paper, we investigate the phase behavior and microstructure for a series of salt-free catanionic surfactants of the type Cm+Cn- with varied chain length mismatch (m not equal n), using light microscopy, DSC, turbidity, surface tension, SAXS and SANS. The compounds consist of alkyltrimethylammonium alkylsulfonates, denoted by TA(m)So(n). Depending on the asymmetry between both ions, three regimes can be identified: (i) weakly asymmetric; (ii) approximately symmetric; and (iii) highly asymmetric. For the TA(16)So(n) compounds, with n = 8 and 9 (weakly asymmetric), the surfactant forms a lamellar phase in water, however, with a striking miscibility gap. This miscibility gap is a consequence of the concentration dependent bilayer charge density. For n = 8, also a temperature-dependent vesicle-to-micelle transition at low surfactant concentration is observed. When the mismatch is low (n = 10) only a non-swelling lamellar phase is formed (approximately symmetric regime). For high mismatch, (n = 6 and 7) an extensive micellar phase is obtained - highly asymmetric regime. Conversely, for the TA(m)So(8) compounds, where m = 12 and 14, the unconventional lamellar miscibility gap and vesicle-micelle transition are again present. These findings are rationalized by considering the effect of film charge density-arising from the chain solubility difference-on the spontaneous curvature and balance of colloidal forces. The type of phase behavior reported here should be extensive to other families of salt-free catanionic amphiphiles, where an appropriate tuning of the solubility mismatch can allow the control of self-assembly.

Abstract In the present work a set of five Ni(II) complexes with general formula [Ni(L)(2)] and with HL = N-thenoylthiocarbamic-O-n-alkylylesters (n = 2-6) has been prepared and characterized in solution by UV-vis and NMR spectroscopies. Three of them were also characterized in the solid state by X-ray diffractometry. The energy rotation of the thiophene ring of ligand was evaluated theoretically. Liposomes of complexes were prepared in order to evaluate their ability to interact with the membrane. Furthermore, their biological activities were evaluated in a set of bacteria (gram+ and gram-) and yeasts. The X-ray structure determination confirms that bidentate ligand forms a tetra co-ordinated complex with an S2O2 co-ordination sphere around the nickel(II) ion in a cis configuration. The metal centre is coordinated in a square planar fashion. NMR spectra taken in solution show a diamagnetic signal compatible with a square-planar geometry around the metal centre. The values obtained for the liposome/water partition coefficients (K-p) show that [Ni(ttete)(2)] and [Ni(ttpre)(2)] have a similar membrane partition ability, whilst the [Ni(ttbue)(2)] derivative presents a significantly higher K-p, describing a stronger interaction within the membrane. For all the compounds, [Ni(ttpre)(2)] has a higher efficacy against Gram negative bacteria and yeasts nevertheless, the anti-yeast and anti-bacterial activity values of all tested compounds are lower than ones of the reference compounds.

Abstract The performance of multivariate curve resolution (MCR-ALS) to decompose sets of excitation emission matrices of fluorescence (EEM) of nanocomposite materials used as analytical sensors was assessed. The two fluorescent nanocomposite materials were: NH(2)-polyethylene glycol (PEG200) functionalized carbon dots, sensible to aqueous Hg(II) (CD); and, CdS quantum dots attached to the dendrimer DAB, sensible to the ionic strength of the aqueous medium (CdS-DAB). The structures of these sets of EEM, obtained as function of the Hg(II) concentration and ionic strength, are characterized by collinear properties (CD) and non-linear spectral variations (CdS-DAB). MCR-ALS was able to detect that the source of the collinearities is the presence of different size CD that show similar affinity towards Hg(II). Moreover, MCR-ALS was able to model the non-linear spectral variations of the CdS-DAB that are induced by varying ionic strength. The chemometric preprocessing of the fluorescent data sets using soft-modelling multivariate curve resolution like MCR-ALS is a critical step to transform these nanocomposites with interesting fluorescent proprieties into analytical useful nanosensors.

Abstract Among new potential solvents for lignocellulosic materials, ionic liquids (ILs) are attracting considerable attention. Hence, the knowledge of the thermophysical properties of such fluids is essential for the design of related industrial processes. Therefore, in this work, a set of thermophysical properties, namely, density, viscosity, and refractive index, as a function of temperature, and isobaric thermal expansivity and heat capacities at a constant temperature, were determined for eight ionic liquids with the 1-ethyl-3-methylimidazolium cation combined with the following anions: acetate, methylphosphonate, methanesulfonate, trifluoromethanesulfonate, dicyanamide, thiocyanate, tosylate, and dimethylphosphate. Imidazolium-based HA were chosen since these are the most studied ionic fluids in biomass dissolution approaches, while a large array of anions was investigated because it was already demonstrated that it is the IL anion that mainly governs the dissolution.

Abstract Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation] ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (Its) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethane-sulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation anion attraction potential. The impact of the cation anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation anion interaction energies determined by mass spectrometry.

Abstract The indiscriminate use of antibiotics in food-producing animals has received increasing attention as a contributory factor in the international emergence of antibiotic-resistant bacteria (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004). Numerous analytical methods for quantifying antibacterial residues in edible animal products have been developed over years (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004; Botsoglou and Fletouris in Handbook of food analysis, residues and other food component analysis, Marcel Dekker, Ghent, 2004). Being Amoxicillin (AMOX) one of those critical veterinary drugs, efforts have been made to develop simple and expeditious methods for its control in food samples. In literature, only one AMOX-selective electrode has been reported so far. In that work, phosphotungstate: amoxycillinium ion exchanger was used as electroactive material (Shoukry et al. in Electroanalysis 6:914-917, 1994). Designing new materials based on molecularly imprinted polymers (MIPs) which are complementary to the size and charge of AMOX could lead to very selective interactions, thus enhancing the selectivity of the sensing unit. AMOX-selective electrodes used imprinted polymers as electroactive materials having AMOX as target molecule to design a biomimetic imprinted cavity. Poly(vinyl chloride), sensors of methacrylic acid displayed Nernstian slopes (60.7 mV/decade) and low detection limits (2.9 x 10(-5) mol/L). The potentiometric responses were not affected by pH within 4-5 and showed good selectivity. The electrodes were applied successfully to the analysis of real samples.

Abstract This work proposes a new biomimetic sensor material for trimethoprim. It is prepared by means of radical polymerization, having trimethylolpropane trimethacrylate as cross-linker, benzoyl peroxide as radicalar iniciator, chloroform as porogenic solvent, and methacrylic acid and 2-vinyl pyridine as monomers. Different percentages of sensor in a range between 1 and 6% were studied. Their behavior was compared to that obtained with ion-exchanger quaternary ammonium salt (additive tetrakis(p-chlorophenyl)borate or tetraphenylborate). The effect of an anionic additive in the sensing membrane was also tested. Trimethoprim sensors with 1% of imprinted particles from methacrylic acid monomers showed the best response in terms of slope (59.7 mV/decade) and detection limit (4.01 x 10(-7) mol/L). These electrodes displayed also a good selectivity towards nickel, manganese aluminium. ammonium, lead, potassium, sodium, iron, chromium, sulfadiazine, alanine, cysteine, tryptophan, valine and glycine. The sensors were not affected by pH changes from 2 to 6. They were successfully applied to the analysis of water from aquaculture.

Abstract Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mV/Delta log([ENR]/M) varied within 48-63. The detection limits ranged from 0.28 to 1.01 mu g mL(-1). Sensors were independent from the pH of test solutions within 4-7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of +/-0.7%), fast response, good sensitivity (47 mV/Delta log([ENR]/M), wide linear range (1.0 x 10(-5)-1.0 x 10(-3) M), low detection limit (0.9 mu g mL(-1)), and a stable baseline for a 5 x 10(-2) M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.