RESUMEN
Herein, we investigate the behavior of the electroactive molecular probe 6-propionyl-2-dimethyl amino naphthalene (PRODAN) in large unilamellar vesicles (LUV) formed with the phospholipid 1,2-di-oleoyl-sn-glycero-3-phosphatidylcholine (DOPC) by using cyclic voltammetry (CV). The CV studies in pure water confirm our previous spectroscopic results that PRODAN self-aggregates due to its low water solubility. Moreover, the electrochemical results also reveal that the PRODAN aggregated species are non-electroactive within the studied electrochemical potential region. In DOPC LUV media, the redox behavior of PRODAN shows how the LUV bilayer interacts with PRODAN aggregated species to form PRODAN monomer species. Moreover, the electrochemical response of PRODAN allows us to propose a model for explaining the electrochemical experimental results and--in conjunction with our measurements--for calculating the value of the partition constant (K(p)) of PRODAN between the water and LUV bilayer pseudophases. This value coincides with that obtained through an independent technique. Moreover, our electrochemical model allows us to calculate the diffusion coefficient (D) for the DOPC LUV, which coincides with the D value obtained through dynamic light scattering (DLS). Thus, our data clearly show that electrochemical measurements could be a powerful alternative approach to investigate the behavior of nonionic electroactive molecules embed in a confined environment such as the LUV bilayer. Moreover, we believe that this approach can be used to investigate the behavior of non-optical molecular drugs embedded in bilayer media.
RESUMEN
Free-base (P), Zn(II) (P(Zn)), Cu(II) (P(Cu)), Pd(II) (P(Pd)), Ni(II) (P(Ni)), and Co(II) (P(Co)) 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl) porphyrins were designed and synthesized to be employed as spectral senzitizers in photoelectrochemical cells. The dyes were studied adsorbed on SnO(2) nanocrystalline semiconductor and also in Langmuir-Blodgett film ITO electrodes in order to disclose the effect of molecular packing on the studied properties. Electron injection yields were obtained by fluorescence quenching analysis comparing with the dyes adsorbed on a SiO(2) nanocrystalline insulator. Back electron-transfer kinetics were measured by using laser flash photolysis. The unmetallized and metallized molecules have different singlet state energies, fluorescence quantum yields, and redox properties. The quantum yields of sensitized photocurrent generation are shown to be highly dependent on the identity of the central metal. It is shown that P(Ni) and P(Co) do not present a photoelectric effect. The other porhyrins present reproducible photocurrent, P(Pd) being the one that gives the highest quantum yield even in closely packet ITO/LB films. Photocurrent quantum yields increase as the dye ground-state oxidation potential becomes more anodic, which is in agreement with the observation, obtained by laser flash photolysis, that back electron-transfer kinetics decrease with the increase in the driving force for the recombination process. This effect could be exploited as a design element in the development of new and better sensitizers for high-efficiency solar cells involving porphyrins and related dyes.
RESUMEN
The electrochemical oxidation of salicylic acid (SA) has been studied on a glassy carbon electrode using cyclic voltammetry and differential pulse voltammetric (DPV) method. SA gives a single irreversible oxidation wave over the wide pH range studied. The irreversibility of the electrode process was verified by different criteria. The mechanism of oxidation is discussed. Using differential pulse voltammetry, SA yielded a well-defined voltammetric response in Britton-Robinson buffer solution, pH 2.37 at 1.088V (versus Ag/AgCl). The method was linear over the SA concentration range: 1-60mugml(-1). The method was successfully applied for the analysis of SA as a hydrolysis product, in solid pharmaceutical formulations containing acetylsalicylic acid (ASA).
RESUMEN
A modified electrode consisting of copper dispersed in a poly-1-naphthylamine (p-1-NAP/Cu) film on a glassy carbon electrode was used as an amperometric detector for the on-line analysis of various carbohydrates separated by high performance liquid chromatography. The results obtained with this new sensor were compared to those obtained with a modified electrode based on the same polymer but with copper ions incorporated at open circuit, as described in a previous paper. In this new modified electrode the copper microparticles were electrochemically deposited into the polymeric matrix by single potential step chronoamperometry. A nucleation and growth mechanism was proposed to explain the current transients of copper electrodeposition. The experimental results were fitted to the proposed mechanism by using a mathematical equation that considers three-dimensional growth and progressive nucleation, assuming a no overlap and no diffusion mechanism. Cyclic voltammetric experiments showed that the electrodeposited copper microparticles provided a catalytic surface suited for the oxidation of glucose and several carbohydrates. The sensitivity of the electrode was influenced by the amount of copper electrodeposited, which in turn depended on the applied overpotential used for the deposition of copper. Liquid chromatographic experiments were carried out to test the analytical performance of these electrodes for the determination of various carbohydrates.
RESUMEN
Dado que en diversos lugares del mundo existen aguas subterráneas con elevadas cantidades de flúor que resultan altamente tóxicas a la salud humana, se están ensayando nuevos métodos alternativos para la eliminación parcial de dicho elemento, utilizando hueso molido