Publications

Abstract The effect on the fluorescence of the europium:tetracycline (Eu:Tc), europium:oxytetracycline (Eu:OxyTc) and europium:chlortetracycline (Eu:ClTc) complexes in approximately 2:1 ratio of nitric oxide (NO), peroxynitrite (ONOO-), hydrogen peroxide (H2O2) and superoxide (O-2 (center dot-)) was assessed at three ROS/RNS concentrations levels, 30 A degrees C and pH 6.00, 7.00 and 8.00. Except for the NO, an enhancement of fluorescence intensity was observed at pH 7.00 for all the europium tetracyclines complexes-the high enhancement was observed for H2O2. The quenching of the fluorescence of the Tc complexes, without and with the presence of other ROS/RNS species, provoked by NO constituted the bases for an analytical strategy for NO detection. The quantification capability was evaluated in a NO donor and in a standard solution. Good quantification results were obtained with the Eu:Tc (3:1) and Eu:OxyTc (4:1) complexes in the presence of H2O2 200 mu M with a detection limit of about 3 mu M (Eu:OxyTc).

Abstract In this work we describe the electrochemical behavior of an ionic liquid formed between choline chloride (ChCl) and chromium chloride hexahidrated (CrCl3 center dot 6H(2)O) in the ratio of 2.5:1 containing 20 wt.% of added ultrapure water, using cyclic voltammetry and chronoamperometry. The reduction of Cr(III) occurs in two steps, Cr(III) to Cr(II) and Cr(II) to Cr(0), respectively. The first step is controlled by diffusion. For the first time a thorough study of the nucleation of chromium from Cr(III) ionic liquid solutions is described. Furthermore for less cathodic potentials there is a diffusion control of nuclei growth. For more cathodic potentials the lattice incorporation of adatoms to the growing nuclei is the limiting process. The additive free bright chromium deposit obtained is formed by semi-spherical nuclei. The effect of hydrogen evolution is only observed for E < - 1.90 V.

Abstract In this work, the ion transfer mechanism of the anticancer drug daunorubicin (DNR) at a liquid/liquid interface has been studied for the first time. This study was carried out using electrochemical techniques, namely cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The lipophilicity of DNR was investigated at the water/1,6-dichlorohexane (DCH) interface, and the results obtained were presented in the form of an ionic partition diagram. The partition coefficients of both neutral and ionic forms of the drug were determined. The analytical parameter for the detection of DNR was also investigated in this work. An electrochemical DNR sensor is proposed by means of simple ion transfer at the water/DCH interface, using DPV as the quantification technique. Experimental conditions for the analytical determination of DNR were established, and a detection limit of 0.80 mu M was obtained.

Abstract Herein, we present a simple microelectrode preparation methodology consisting in coating a platinum wire or a carbon fiber with a thin insulating Parylene C film (e.g. 1-10 mu m), to produce SECM probes with a small and constant probe RG (i.e. ratio between the radius of the insulating sheath and the radius of the active electrode area). After exposition of a fresh active electrode area by blade cutting, a disc shaped electrode is obtained thanks to a protective hot mounting wax layer that avoids Parylene C coating deformation and is easily removed with acetone. Stiffness and straightness of the probe can be tuned by modifying the Parylene C coating thickness and the length of the carbon fiber or platinum wire. This simple electrode preparation method is highly reproducible (c.a. > 90%). The prepared Parylene C coated microelectrodes were characterized by optical microscopy, cyclic voltammetry, scanning electrochemical microscopy (SECM) approach curves and finally applied to SECM imaging of Pt band structures in contact-less and contact mode.

Abstract A novel optical fiber sensor is presented for measuring dissolved CO2 for water quality monitoring applications, where the optical signal is based either on refractive index changes or on color change. The sensing chemistry is based on the acid-basic equilibrium of 4-nitrophenol, that is converted into the anionic form by addition quaternary ammonium hydroxide. The CO2 sensitive layer was characterized and tested by using simple absorbance/reflectance measurement setups where the sensor was connected to a fiber optic CCD spectrometer. A prototype simulating a real shallow raceway aquaculture system was developed and its hydraulic behavior characterized. A commercially available partial-pressure-NDIR sensor was used as a reference for dissolved CO2 tests with the new optical fiber sensor under development. Preliminary tests allowed verifying the suitability of the new optical sensor for accurately tracking the dissolved carbon dioxide concentration in a suitable operation range. Direct comparison of the new sensor and the reference sensor system allowed to demonstrate the suitability of the new technology but also to identify some fragilities there are presently being addressed.

Abstract Gold nanoparticle (Au NP) mirrors, which exhibit both high reflectance and electrical conductance, were self-assembled at a [heptane + 1,2-dichloroethane]/water liquid/liquid interface. The highest reflectance, as observed experimentally and confirmed by finite difference time domain calculations, occurred for Au NP films consisting of 60 nm diameter NPs and approximate monolayer surface coverage. Scanning electrochemical microscopy approach curves over the interfacial metallic NP films revealed a transition from an insulating to a conducting electrical material on reaching a surface coverage at least equivalent to the formation of a single monolayer. Reflectance and conductance transitions were Interpreted as critical junctures corresponding to a surface coverage that exceeded the percolation threshold of the Au NP films at the [heptane + 1,2-dichloroethane]/water interface.

Abstract The decomposition reaction of dimethyl-1,2-dioxetanone in dichloromethane was studied by using a DFT approach. The low efficiency of triplet and singlet excited-state formation was rationalised. A charge-transfer process was demonstrated to be involved in the chemiluminescence process. Present and previous results allow us to define an interstate crossing-induced chemiexcitation (ICIC) mechanism for the chemiluminescence of dioxetanones. Charge transfer is needed to reach a transition state, in the vicinity of which direct population of excited states is possible. The chemiexcitation process is then governed by singlet/triplet intersystem crossings. Structural modifications then modify the rate of these crossings and the singlet ground and excited-state interaction, thereby modulating the efficiency of this process and the spin of the resulting products.

Abstract Macromolecules, such as polyethylene glycol (PEG), have been frequently used in the preparation of xerogels, mainly with the purpose of tuning the meso- or macroporosity. However, PEG has never been applied in the context of the preparation of molecularly imprinted xerogels for small molecules. Thus, we decided to conduct a computational and experimental study of the incorporation of PEG into formerly studied sol-gel mixtures for the preparation of damascenone-imprinted xerogels. Computationally, two types of pregelification models were studied, one representing the initial mixture (SI3/SIPA:S:3 models) and the other representing the same mixtures after considerable solvent loss (SI3/SIPA:40:1 models). The latter ones were particularly prolific in providing clear effects of the PEG. In the SI3:40:1 model (containing SI3 units of Si3O3(OH)(6) mimicking the final xerogels backbone), a prohibitive instead of a promoting effect of PEG on the template-SI3 association was observed. PEG was found to interpose the SI3 aggregates, turning them smaller and more disperse. In agreement with that, a much higher porosity and surface area were found for the corresponding xerogel prepared with PEG, while no appreciable improvement of the imprinting efficiency could be observed. In the SIPA:40:1 model (containing both SI3 and SIPA units; SIPA, Si3O3(OH)(5)C3H6NHC6H5, representing the introduction of the organic functional group into the xerogel network), the interactions related to the network structuring were not significantly affected. This was due to the fact that the SIPA units themselves had a dispersive effect on the silica network; the PEG molecules were "pushed" into the aqueous/methanolic continuum, and their presence was somewhat redundant. Accordingly, both prepared SIPA-xerogels (with PEG or not) exhibited higher porosity compared to SI3-xerogels. Although the simulation results were not conclusive about the effect of PEG on the template-functional group association, experimentally it was clear that the imprinting effect was not improved with PEG.