A. Fernando Silva

Solid-phase microextraction Ni-Ti fibers coated with functionalised silica particles immobilized in a sol-gel matrix

One of the possible approaches for the development of novel solid-phase microextraction (SPME) fibers is the physical deposition of porous materials onto a support using high-temperature epoxy glue. However, a major drawback arises from decomposition of epoxy glue at temperatures below 300 degrees C and instability in some organic solvents. This limitation motivated us to explore the possibility of replacing the epoxy glue with a sol-gel film, thermally more stable and resistant to organic solvents. We found that functionalised silica particles could be successfully attached to a robust Ni-Ti wire by using a UV-curable sol-gel film. The particles were found to be more important than the sol-gel layer during the microextraction process, as shown by competitive extraction trials and by the different extraction profiles observed with differently functionalised particles. If a quality control microscopic-check aiming at the rejection of fibers exhibiting unacceptably low particle load was conducted, acceptable (6-14%) reproducibility of preparation of C(18)-silica fibers was observed, and a strong indication of the durability of the fibers was also obtained. A cyclohexyldiol-silica fiber was used, as a simple example of applicability, for the successful determination of benzaldehyde, acetophenone and dimethylphenol at trace level in spiked tap water. Recoveries: 95-109%; limits of detection: 2-7 microg/L; no competition effects within the studied range (<or=125 microg/L).

Influence of the extraction process on the rheological and structural properties of agars.

Agars obtained by traditional hot-water (TWE) and microwave-assisted (MAE) extractions were compared in terms of their rheological and physicochemical properties and molecular self-association in solutions of low (0.05%, w/w) and high (1.5%, w/w) polymer concentrations. At low concentration, thin gelled layers were imaged by AFM. Slow or rapid cooling of the solutions influenced structure formation. In each case, TWE and MAE agar structures were different and apparently larger for MAE. At high concentration, progressive structural reinforcement was seen; while TWE agar showed a more open and irregular 3D network, MAE agar gel imaged by cryoSEM was denser and fairly uniform. The rheological (higher thermal stability and consistency) and mechanical (higher gel strength) behaviors of MAE agar seemed consistent with a positive effect of molecular mass and 3,6-anhydro-α-l-galactose content. MAE produced non-degraded agar comparable with commercial ones and if properly monitored, could be a promising alternative to TWE.

Electro-assisted solvent extraction of Cu2+, Ni2+ and Cd2+

Abstract A novel separation method, i.e. electro-assisted solvent extraction, based on the principles of two-phase electrochemistry, has been demonstrated for the successful separation of Ni 2+ , Cu 2+ and Cd 2+ ions. 2-Heptanone has been used as the organic solvent for the transfer of Ni 2+ , Cu 2+ and Cd 2+ facilitated by 2,2′;6′,2″-terpyridine. It is shown that extraction efficiency depends on the concentration ratio of ligand to metal ion and importantly, on the applied interfacial potential difference. It was found that Ni 2+ (not Cd 2+ or Cu 2+ ) extraction is suppressed in the presence of Mg 2+ ion due to competitive complexation.

Zn–Sn electrodeposition from deep eutectic solvents containing EDTA, HEDTA, and Idranal VII

The use of deep eutectic solvents for metal electrodeposition has become an area of interest in the recent years. In this study, ethaline, propeline, and reline were used as solvents for the electrodeposition of Sn–Zn alloys. Ethaline, propeline, and reline displayed identical voltammetric profiles for the reduction of Zn(II) and Sn(II). Further studies were carried out in ethaline which is the liquid with lowest viscosity. To improve physical and morphological properties of the Sn–Zn deposits, additives were added to the ionic liquid solution. In this study, the addition of three chelators (EDTA, HEDTA, and Idranal VII) and their effects on the voltammetric behavior of zinc and tin and the resultant morphology was described. The structure and composition of the Zn–Sn deposit was largely affected by the additives with the largest effect being obtained in the presence of Idranal VII.

Solanum nigrum L. weed plants as a remediation tool for metalaxyl-polluted effluents and soils

In this work, the phytoremediation potential of metalaxyl, a commonly used persistent, mobile and leachy fungicide, by Solanum nigrum L. plants was studied. The study revealed that this plant species can be used as an excellent metalaxyl phytoremediation tool, thus providing a cost effective and environmentally friendly clean technology for the decontamination of sites and effluents. As it can be sowed directly in the remediation site, is able to complete its life cycle without suffering major stress. Because it accumulates high amounts of the fungicide in the aboveground tissues, enables its concentration and proper disposal by cutting off the corresponding plant part. The study also suggests that the tolerance to metalaxyl is due to a suitable antioxidant response comprising proline accumulation and guaiacol peroxidase and glutathione-S-transferase enhanced activities, that reduce oxidative damage to the plant organs.

The electrical double layer at the ionic liquid/Au and Pt electrode interface

The role of the electrode material on the interfacial double layer structure of a series of ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM][PF6]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4MIM][Tf2N]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([C4MIM][BF4]) was investigated on gold (Au) and platinum (Pt) electrodes. The aim of this work is to contribute with experimental data to complement theoretical models that are currently under discussion in order to describe the structure of the double layer formed at the interface electrode/ionic liquid. There is still a controversy about the general shape that differential capacitance curves should present and researchers still continue making efforts to correlate the nature of the electrode/ionic liquid with the shape of the curves. Differential capacitance curves at the Au and Pt interface shows that the values of capacity follow the same order C [C4MIM][PF6] < C [C4MIM][Tf2N] < C [C4MIM][BF4]. However, the values of C are considerably lower for Pt when compared with Au for all three liquids studied. The alkyl chain length effect on the differential capacity curves was also studied at the Pt/[CnMIM][Tf2N] interface (where n = 2, 4 and 6). The results follow an expected trend except for the liquid [C6MIM][Tf2N] that shows a value of capacity near to that obtained for [C2MIM][Tf2N]. Since ionic liquids have great applicability in energy storage devices and capacitors it is of great importance to evaluate the dependence of differential capacitance as function of temperature. The results indicate that the capacity increases with increasing temperature for all systems studied in this work.

Aggregation-induced conformational transitions in bovine β-lactoglobulin adsorbed onto open chitosan structures

Chitosan is a natural polysaccharide which strongly interacts with whey proteins in solution. Certain protein–polyelectrolyte complexes and electrostatically assembled thin films have been shown to be good platforms for the preservation of globular and small proteins in their native state mainly due to the hydrophilic nature of these polyelectrolytes and to the lack of physical space for embedded proteins to relax. As a consequence, the use of natural polyelectrolytes in new nanocomposite materials for medicine, chemical analysis, catalysis, etc. has exploded in the last few years. Nevertheless, in many of these applications proteins are immobilized in more open structures without physical restrictions to undergo conformational changes. In this work, we investigate the nature of these transitions for a model whey protein, β-LG, on a chitosan-decorated Au surface in a scenario for which protein–surface interactions compete with boosted protein–protein non-coulombic forces. The adsorption kinetics, protein mass uptake (plus associated water), and flexibility of the adsorbed layers have been followed in situ by the quartz crystal microbalance with dissipation monitoring (QCM-D). Further ex situ characterization has been performed by atomic force microscopy (AFM) and non-invasive scanning electron microscopy (SEM). The balance between both types of interactions yielded surfaces heavily loaded with protein and water in which orientational transitions seemed restricted. The kinetics of the process was registered in a wide range of concentrations and successfully fitted to a double exponential equation derived from the RSA theory accounting for the establishment of slow post-adsorption conformational transitions.

Chromatographycally efficient microspherical composites of molecularly imprinted xerogels deposited inside mesoporous silica

A different approach to the preparation of microspheric particles of molecularly imprinted xerogels (MIX) is presented here. The technique consisted of filling up the pores of spherical, mesoporous, bare silica particles with a pregelification mixture by applying pressure. Upon gelification and drying, thin layers of MIX were deposited on the mesopores. Spherical composites of S-naproxen (S-NAP) imprints were produced by following this simple strategy. The performance of the imprints was quite satisfactory in terms of recognition ability (ascertained by selectivity against ibuprofen, α=4.9, and an imprinting factor of 13) whereas an outstanding improvement on dynamic features (expressed as column efficiency), as compared to the corresponding bulk format MIX (9 vs. 1.2 theoretical plates/cm), was reached.

Probing the Contribution of Different Intermolecular Forces to the Adsorption of Spheroproteins onto Hydrophilic Surfaces

Protein adsorption is a delicate process, which results from the balance between the properties of proteins and their solid supports. Although the relevance of some of these parameters has been already unveiled, the precise involvement of electrostatics and other weaker intermolecular forces requires further comprehension. Aiming to contribute to this task, this work explores the attachment, rearrangement, and surface aggregation of a model spheroprotein, such as bovine β-lactoglobulin (β-LG), onto hydrophilic substrates prefunctionalized with different alkylthiol films. Thereby, a variety of electrostatic scenarios for the adsorption of β-LG could be recreated through the variation of the pH and the functional chemistry of the surfaces. The changes in surface mass density (plus associated water) and film flexibility were followed in situ with quartz crystal microbalance with dissipation monitoring. Film packing and aggregation were assessed by faradaic electrochemical measurements and ex situ atomic force microscopy and field effect scanning electron microscopy. In contrast to previous hypotheses arguing that electrostatic interactions between charged substrates and proteins would be the only driving force, a complex interplay between Coulombic and non-Coulombic intermolecular forces (which would depend upon the experimental conditions) has been suggested to explain the results.

Cationic imprinting of Pb(II) within composite networks based on bovine or fish chondroitin sulfate

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.