Phyllosilicate-content influence on the spectroscopic properties and antioxidant capacity of Iberian Cretaceous clays.

Kaolinite-rich Cretaceous clay sediment samples from Burgos (Spain) have been analyzed by elemental analysis, X-ray fluorescence, inductively coupled plasma mass spectrometry, X-ray diffraction and different spectroscopic techniques, as Fourier Transform Infrared, ultraviolet-visible and electron paramagnetic resonance. The clay sediment samples mainly contain quartz, muscovite and kaolinite. Different radicals, as A- and B-Centers in kaolinite and organic paramagnetic species, are detected. An illite/kaolinite FTIR band ratio parameter (IKB) is proposed to infer the illite/kaolinite proportion, which can be useful to graphically visualize the iron-substituted Al(III) sites. Studies of the activity as scavengers of DPPH and ABTS radicals show that samples with a larger amount of orthorhombic Fe(III) ions replacing Al(III) ions exhibit a higher antioxidant capacity.

Carbon nanostructured films modified by metal nanoparticles supported on filtering membranes for electroanalysis.

A novel methodology to prepare sensors based on carbon nanostructures electrodes modified by metal nanoparticles is proposed. As a proof of concept, a novel bismuth nanoparticle/carbon nanofiber (Bi-NPs/CNF) electrode and a carbon nanotube (CNT)/gold nanoparticle (Au-NPs) have been developed. Bi-NPs/CNF films were prepared by 1) filtering a dispersion of CNFs on a polytetrafluorethylene (PTFE) filter, and 2) filtering a dispersion of Bi-NPs chemically synthesized through this CNF/PTFE film. Next the electrode is prepared by sticking the Bi-NPs/CNF/PTFE film on a PET substrate. In this work, Bi-NPs/CNF ratio was optimized using a Cd2+ solution as a probe sample. The Cd anodic stripping peak intensity, registered by differential pulse anodic stripping voltammetry (DPASV), is selected as target signal. The voltammograms registered for Cd stripping with this Bi-NPs/CNF/PTFE electrode showed well-defined and highly reproducible electrochemical. The optimized Bi-NPs/CNF electrode exhibits a Cd2+ detection limit of 53.57 ppb. To demonstrate the utility and versatility of this methodology, single walled carbon nanotubes (SWCNTs) and gold nanoparticles (Au-NPs) were selected to prepare a completely different electrode. Thus, the new Au-NPs/SWCNT/PTFE electrode was tested with a multiresponse technique. In this case, UV/Vis absorption spectroelectrochemistry experiments were carried out for studying dopamine, demonstrating the good performance of the Au-NPs/SWCNT electrode developed.

Development of a Novel Bidimensional Spectroelectrochemistry Cell Using Transfer Single-Walled Carbon Nanotubes Films as Optically Transparent Electrodes.

A really easy method to transfer commercial single-walled carbon nanotubes (SWCNTs) to different substrates is proposed. In this paper, a homogeneous transference of SWCNTs films to nonconductor and transparent supports, such as polyethylene terephthalate, glass, and quartz, and to conductor supports, such as indium tin oxide, aluminum, highly ordered pyrolytic graphite, and glassy carbon, was achieved using a very fast, reproducible, and clean methodology. In order to test these transferences, SWCNTs films transferred on quartz were used as working optically UV-vis transparent electrodes due to their optimal electrical and optical properties. A new easy-to-use, homemade optical fiber based cell for bidimensional spectroelectrochemistry was developed, offering the possibility to measure in normal and parallel configuration. The cell was tested with ferrocenemethanol, a compound widely used in electrochemistry but scarcely studied by spectroelectrochemistry, covering the UV-vis spectral region.

Optical fiber spectroelectrochemical device for detection of catechol at press-transferred single-walled carbon nanotubes electrodes.

A new long-optical-pathway spectroelectrochemical cell for absorptometric measurements in the UV-Vis region was developed. This cell consists of two optical fibers brought face to face and fixed on the working electrode support. As a proof of concept, the spectroelectrochemical cell was applied to the determination of catechol using a press-transferred single-walled carbon nanotube film as the working electrode. Voltabsorptometry was demonstrated to be very helpful in understanding the mechanism of catechol oxidation. The experiments showed that the main oxidation product is o-benzoquinone, but other soluble side products are also observed. Multivariate calibration explains the selection of 390 nm as the best wavelength for the univariate absorptometric determination of catechol, avoiding the interference of oxidation side products. Catechol was quantified using both the electrochemical and the spectroscopic signal, demonstrating that this hybrid technique is an autovalidated analytical method. Dual detection of catechol was also carried out using amperometric spectroelectrochemistry. Finally, spectroelectrochemistry was used to quantify catechol in the presence of hydroquinone.

Electropolymerization and characterization of polyaniline films using a spectroelectrochemical flow cell.

A new spectroelectrochemical flow cell is presented and its capability to provide a better understanding of reaction mechanisms is illustrated with the study of the electrosynthesis and characterization of a conducting polymer, polyaniline (PANI). A spectroelectrochemical study of electropolymerization of aniline under flow conditions has been performed for the first time. The significant influence that the flow rate of feeding monomer solution has on the electropolymerization process and, consequently, on the electrochromic properties of the resulting polymer has been demonstrated.

Analysis and speciation of arsenic by stripping potentiometry: a review.

This paper provides a review that summarizes several examples of the literature from 1980 to 2003, to illustrate the applications of stripping potentiometry for the determination and speciation of arsenic in several samples. A discussion on the main advantages of stripping potentiometry in comparison with other electrochemical methods employed for arsenic determination is presented. Special attention is devoted to stripping modes (constant current or chemical stripping) and to issues related to the choice of working electrodes and supporting electrolyte. This approach has been also applied at arsenic determination in flow systems. A section is dedicated to speciation of arsenic and total arsenic determination and other to analytical characteristic of method and their interferences. An extensive compilation, organize by experimental and analytical parameters and real sample studied is presented.

A continuous flow system design for simultaneous determination of heavy metals in river water samples.

A new design of a continuous flow system applied to the simultaneous determination of the concentration of zinc(II), cadmium(II), lead(II), copper(II), nickel(II), cobalt(II) and chromium(VI) in river water is described. A flow cell made in the laboratory, which has been patented, based on a 'wall-jet' configuration with a three-electrode system is described. Optimum conditions for the determination of the metal ions are reported. The detection limits and relative standard deviation values were 4.01x10(-9) M and 0.078 for Zn(II), 1.76x10(-10) M and 0.056 for Cd(II), 4.69x10(-10) M and 0.134 for Pb(II), 2.29x10(-10) M and 0.138 for Cu(II), 1.61x10(-9) M and 0.093 for Ni(II), 1.91x10(-9) M and 0.113 for Co(II), and 1.35x10(-9) M and 0.081 for Cr(VI). The procedure was applied to a sample of water from the Arlanzón river and the results were compared with inductively coupled mass plasma spectrometry (ICP-MS) as reference method. The final aim of this work is to design a flow system, which can be automated.