Study of the effect of the membrane composition on ion transfer across a supported liquid membrane
Abstract The rate of ion transfer across the supported liquid membrane (SLM) is studied in the rotating diffusion cell (RDC), varying the chemical composition of the SLM from net-cloth supported gel membranes to radiation-grafted polymer membranes. Steady-state current–voltage curves are measured as a function of the rotation rate, and values for the standard rate constant, k 0 , are determined for a series of tetraalkylammonium cations from the analysis of the initial slopes and the diffusion limiting currents. The analysis gives values for k 0 of the order of 10 −2 –10 −4 cm s −1 , which is in rather good agreement with the values found in the literature for this type of the system. As co…
Thermodynamic analysis of binding between drugs and glycosaminoglycans by isothermal titration calorimetry and fluorescence spectroscopy
The thermodynamics of the interaction of positively charged drug molecules with negatively charged glycosaminoglycans (GAGs) is investigated by isothermal titration calorimetry (ITC) and fluorescence spectroscopy. The drugs considered are propranolol hydrochloride, tacrine, and aminacrine, and the polymers used as model GAGs are dextran sulfate, chondroitin sulfate, and hyaluronic acid. The ITC results show that the interaction between drugs and GAGs is via direct binding and that GAGs bind to drugs at one set of sites. Large negative values of heat capacity change (DeltaC(p)) are observed upon binding of GAGs to drugs. Such negative DeltaC(p) is not expected for purely electrostatic intera…
Soret coefficient of trace ions determined with electrochemical impedance spectroscopy in a thin cell. Theory and measurement
The tendency of a substance to migrate due to a temperature gradient is known as thermodiffusion or the Soret effect. We believe that this is the first work that describes the study of the Soret effect using electrochemical impedance spectroscopy in a non-isothermal thin cell, and shows how the Soret coefficient can be determined from these measurements. The effect of a temperature gradient in a thin cell is analyzed, both theoretically and experimentally. Our theoretical modeling of the system predicts the effect of key parameters to the impedance spectra. Experimentally we determine the Soret coefficient of the redox couple Fe(CN)64−/Fe(CN)63− in an aqueous KCl solution. It is found that …
Preparation of nanostructures composed of dextran sulfate/ruthenium nanoparticles and their interaction with phospholipid monolayers at a liquid–liquid interface
Abstract Nanostructures composed of dextran sulfate (DS)/ruthenium (Ru) nanoparticles (NPs) adsorbed on phospholipid monolayers at a liquid–liquid interface were prepared and characterized electrochemically in relation to their potential use in drug delivery systems. First, positively charged Ru NPs were prepared, and then negatively charged DS was adsorbed on the surface of the NPs, thus forming well-defined and organized structures, as observed under the transmission electron microscope, which are referred to composite nanoclusters. The lipid monolayers were formed by depositing either 1-palmitoyl-2-oleoyl- sn -glycero-3-phosphatidylcholine or 1-palmitoyl-2-oleoyl- sn -glycero-3-phospho- …
Thermodiffusion of sodium polystyrene sulfonate in a supporting electrolyte
Thermodiffusion, or the Soret phenomenon, is well understood in simple systems, but in multicomponent and polyvalent electrolyte systems the process becomes more complicated due to the coupling of fluxes. We experimentally investigate the time evolution of a concentration gradient generated by thermodiffusion of a polyelectrolyte (poly(sodium 4-styrene sulfonate), NaPSS) in a 1:1 supporting electrolyte. We also derive and solve the transport equations that are used to extract the Soret coefficient from the experimental observations. It is shown that NaPSS thermodiffusion in NaCl is strongly dependent on concentration, with almost 100% thermal separation in concentrations below 15 nmol L−1. …
Ion Pairing in the Analysis of Voltammetric Data at the ITIES: RbTPB and RbTPBCl in 1,2-dichloroethane
The association of rubidium-tetraphenylborate (RbTPB) and rubidium-tetrakis(-chlorophenyl)borate (RbTPBCl) ion pairs in the organic solvent 1,2-dichloroethane (DCE) have been obtained from condutivity and voltammetric data. Conductivity measurements given K RbTPBCl =43 100 M -1 and yield a lower bound for K RbTPB (K RbTPB > 70000 M -1 ). The latter association constant is at variance with the previously accepted value. A method for analysing voltammetric data which allows for the determination of the association constants is presented. The positive polarization limit where the transfer of Rb + takes place is shifted by ca. 200 mV when changing the anion of the organic base electrolyte from …
Electrochemical study of copper chloride complexes in the RTIL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide
The electrochemistry of copper(I) and copper(II) chloride complexes in the RTIL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, BMPTf2N, has been studied with constant current electrolysis and cyclic staircase voltammetry at temperatures between 21.0 and 96.0 °C and in different concentrations of chloride. The chloride concentration was controlled by addition of 1-butyl-1-methylpyrrolidinium chloride, BMPCl. An important finding is the evidence of a three-coordinated complex, Cu(I)Cl32− which has not been found in organic chloroaluminates without a significant increase in temperature. Two Cu(I) species were found at molar ratios of [Cl−]/[Cu] < 4. The kinetic parameters for…
Ion-exchange fibers and drugs: a transient study.
The objective of this study was to theoretically model and experimentally measure the kinetics and extent of drug release from different ion-exchange materials using an in-house-designed flow-cell. Ion-exchange fibers (staple fibers and fiber cloth) were compared with commercially available ion-exchange materials (resins and gels). The functional ion-exchange groups in all the materials were weak -COOH or strong -SO3H groups. The rate and extent of drug release from the fibers (staple fiber>fiber cloth) was much higher than that from the resin or the gel. An increase in the hydrophilicity of the model drugs resulted in markedly higher rates of drug release from the fibers (nadolol>metoprolo…
Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface.
Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene−water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyr- in, 4,5-bis(5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl))-9,9-dimethylxanthene, Co2(DPX), actually catalyzes oxygen reduction to hydrogen p…
Thermal potential of ion-exchange membranes and its application to thermoelectric power generation
The low efficiency and high price of thermoelectric semiconductors has generated interest in unconventional forms of thermoelectric materials. In this article, ionic thermoelectricity has been studied with commercial ion-exchange membranes for different aqueous 1:1 electrolytes. The theory of thermal membrane potential has been derived taking into account the ionic heats of transport, the non-isothermal Donnan potentials, the temperature polarization, and the thermally-induced concentration polarization of the electrolyte. Also the generated thermoelectric power has been experimentally studied. The experiments show good agreement with the theory, and suggest ways for systematic improvement …