Interface Between Two Immiscible Electrolyte Solutions Research Articles

Proton-Coupled Oxygen Reduction at Liquid−Liquid Interfaces Catalyzed by Cobalt Porphine

Cobalt porphine (CoP) dissolved in the organic phase of a biphasic system is used to catalyze O(2) reduction by an electron donor, ferrocene (Fc). Using voltammetry at the interface between two immiscible electrolyte solutions (ITIES), it is possible to drive this catalytic reduction at the interface as a function of the applied potential difference, where aqueous protons and organic electron donors combine to reduce O(2). The current signal observed corresponds to a proton-coupled electron transfer (PCET) reaction, as no current and no reaction can be observed in the absence of either the aqueous acid, CoP, Fc, or O(2).

Voltammetry for surface-active ions at polarisable liquid|liquid interfaces

Adsorption of charged species at the interface between two immiscible electrolyte solutions (ITIES) is simulated taking into account both the mutual influence between the potential dependent surface excess charge and the potential distribution between the two phases and the partition equilibrium of the surface-active molecules. The electrical potential profiles are calculated assuming a single adsorption plane separating two electrical diffuse layers following the modified Verwey–Niessen model (MVN). The interfacial boundary potential is obtained from the electroneutrality condition. The interplay between adsorption and partition under steady-state conditions is addressed yielding voltammetric responses for the adsorption–desorption processes along with the faradaic response.

Effect of α-Cyclodextrin on Drug Distribution Studied by Electrochemistry at Interfaces between Immiscible Electrolyte Solutions

The description and understanding of noncovalent interactions and distribution of potential new drug compounds in an organism is of paramount importance for the successful development of new drugs. In this work, a new procedure based on electrochemistry at the interface between two immiscible electrolyte solutions (ITIES) for addressing and discriminating between drug compound/ligand interactions in aqueous solution and nonspecific ligand effects on oil-water distribution behavior has been developed. The procedure is demonstrated using five drug compounds with different physical chemical parameters and alpha-cyclodextrin as the aqueous phase ligand. Alpha-cyclodextrin was chosen as an aqueous phase ligand, as it is frequently used in drug formulations to enhance solubility and bioavailability of drug compounds. Supplementary capillary electrophoresis experiments provided more detailed information on alpha-cyclodextrin drug complexation and, in combination with the electrochemical studies, provided information on solvation effects affecting the oil-water distribution of the drug compounds. The use of ligand shift ion partition diagrams for data presentation is a convenient format for the visualization of ligand effects on distribution behavior of related drug compounds.

Bioanalytical Detection Based on Electrochemistry at Interfaces between Immiscible Liquids

The electrochemical properties of the interface between two immiscible electrolyte solutions (ITIES) have been studied intensely for more than 30 years now. Although there has always been an interest in the analytical applications of this electrochemical behavior, the opportunities it affords for the detection of biomolecular species, in particular, have become of increased interest in recent years. This mini-review discusses recent advances in this bioanalytical arena, highlighting the detection of molecules ranging from low-molecular-mass bioorganic substances (e.g., neurotransmitters, amino acids, drugs) through to proteins and nucleic acids.

Electrochemically Modulated Liquid−Liquid Extraction of Ionized Drugs under Physiological Conditions

Electrochemically modulated liquid-liquid extraction (EMLLE) enables the selective extraction and separation of ions from mixtures by choice of an applied interfacial potential difference. The extraction of ionized drugs from artificial urine is reported in this paper. The artificial urine matrix was characterized by cyclic voltammetry at the interface between two immiscible electrolyte solutions (ITIES), showing that components of that aqueous phase truncate the available potential window at the ITIES. The transfer of three cationic drugs from aqueous artificial urine to the 1,2-dichloroethane organic electrolyte phase was examined. Both propranolol and timolol were found to transfer across the artificial urine-organic interface. However, sotalol transfer was not possible within the available potential window. Extraction of propranolol and timolol from artificial urine into an organogel phase, by electrochemically modulated liquid-liquid extraction, was examined. The application of potentials positive of the drugs' formal transfer potentials enabled the selective extraction of both propranolol and timolol, with a higher potential being required for timolol. This work demonstrates the practical utility of EMLLE for the selective extraction of target compounds from a complex sample matrix.

Derivation of the explicit equation relating mass-transport-limited-current to voltage at the interface between two immiscible electrolyte solutions (ITIES)

The potential drop between two immiscible electrolyte solutions consists of the sum of that across the double layer and the diffusion barrier layer. A relation between these components has been proposed by Indenbom. We extended his approach to give a relation between the current density and the overall potential drop between the two bulk solutions. The final expression is mathematically similar to the Butler–Volmer equation for classical electrode kinetics.

Electrochemical Study of Insulin at the Polarized Liquid−Liquid Interface

This paper reports on the electrochemical behavior of bovine insulin at the interface between two immiscible electrolyte solutions (ITIES). The voltammetric ion-transfer response obtained in the presence of insulin was dependent on the aqueous phase pH conditions and on the nature of the organic phase electrolyte employed in experiments. Optimal detection was obtained at acidic pH below the isoelectric point of insulin where it was positively charged. A shift in transfer potentials to lower potential values was observed with decreasing hydrophobicity of the anion of the organic phase electrolyte. No ion-transfer response was observed at pH values of the aqueous phase above the isoelectric point, where insulin was negatively charged. These results suggest that the voltammetric response is due to ion-pairing interactions at the ITIES between positively charged insulin and the hydrophobic anion of the organic phase electrolyte, together with adsorption of the ion-pair at the interface. The voltammetric response was obtained for insulin at concentrations down to 1 muM. These results show that electrochemistry is useful in studying the behavior of this important protein molecule at the polarized water-1,2-DCE interface and provides an alternative detection mode for bioanalytical applications.

Study of electrochemical phosphate sensing systems: Spectrometric, potentiometric and voltammetric evaluation

Characterization of the interaction of a urea-functionalized calix[4]arene ionophore and phosphate was undertaken by combination of nuclear magnetic resonance (NMR) spectrometry, potentiometric selectivity coefficient evaluation and voltammetric ion transfer at the interface between two immiscible electrolyte solutions (ITIES). NMR revealed that the urea protons were involved in complexation with the target anion and potentiometric separate solution selectivity data indicated selectivity for phosphate over chloride and sulphate. Voltammetry at the ITIES confirmed that the ionophore-facilitated transfer of monohydrogen phosphate occurred in preference to dihydrogen phosphate transfer. The results correlate with previously reported data on the potentiometric evaluation of this calixarene as an anionophore in PVC-membrane electrodes. The data provide the basis for development of amperometric monohydrogen phosphate sensors based on the ion-transfer principle.

Scanning Electrochemical Microscopy. 58. Application of a Micropipet-Supported ITIES Tip To Detect Ag+ and Study Its Effect on Fibroblast Cells

We report the use of a micropipet-supported ITIES (interface between two immiscible electrolyte solutions, also called a liquid/liquid (L/L) or water/oil (W/O) interface) as a scanning electrochemical microscopy (SECM) tip to detect silver ion and explore Ag+ toxicity in living cells. A 1,2-dichloroethane solution containing a commercially available calixarene-based Ag+ ionophore (IV) was injected into a micrometer-size glass pipet to construct an Ag+-selective SECM tip. The local Ag+ concentration, down to the micromolar level, in the vicinity of living fibroblast cells, was monitored by SECM approach curves and through imaging of the uptake and efflux of Ag+ by living fibroblast cells in real time. The results show that several stages of interaction between Ag+ and fibroblast cells exist. Since a number of biological processes of cells are involved with non-redox-active ions, the work presented here provides a new way to explore cell metabolism, drug delivery, and toxicity assessment by SECM.

Electrochemistry of Non-Redox-Active Poly(propylenimine) and Poly(amidoamine) Dendrimers at Liquid−Liquid Interfaces

The electrochemistry of a series of dendrimers was examined at the interface between two immiscible electrolyte solutions (ITIES), enabling study of non-redox-active dendrimers. Different generations of poly(propylenimine) (DAB-AM-n) and poly(amidoamine) (PAMAM) dendrimers were studied. In their protonated states, the dendrimers were transferred across the ITIES, with the electrochemical behavior observed depending on the dendrimer family, the generation number, and the experimental pH. The electrochemistry of the lower generations studied was characterized by well-defined peaks for both dendrimer families and with small peak-peak separations in the case of the PAMAM family. The voltammetry of the higher generations was more complex, showing distorted voltammograms and instability of the interface. The charges of the transferring dendrimers were calculated by convolution of the voltammetric data and were similar to the theoretical charges for DAB-AM-n. For PAMAM, only the lowest generation exhibited reversible behavior, with higher generations having irreversible behavior. Using cyclic voltammetry, low micromolar concentrations of the dendrimers were detected. The results show that electrochemistry at the ITIES can be a useful method for characterization of ionizable dendrimers and that voltammetry can be a simple method for detection of low concentrations of these multicharged species.

Evaluation of the lipophilic properties of opioids, amphetamine-like drugs, and metabolites through electrochemical studies at the interface between two immiscible solutions

For the first time, the partition coefficients of the ionized forms of several opioids, amphetamine-like drugs, and their metabolites were determined by studying their ionic transfer process across the bare interface water∣organic solvent. The ionic partition coefficients of the monocationic forms of 12 compounds—heroin, 6-monoacetylmorphine (6-MAM), morphine, acetylcodeine, codeine, dihydrocodeine, methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine (MDMA or “ecstasy”), 3,4-methylenedioxyamphetamine (MDA), 3-methoxy-α-methyldopamine (3- OMe-α-MeDA), and α-methyldopamine (α-MeDA)—were attained using electrochemical measurements, by cyclic voltammetry, at the interface between two immiscible electrolyte solutions (ITIES). Then the acquired lipophilicity values were correlated to the chemical structure of the compounds and with the metabolic pathways central to each class of drugs. Although the mechanisms of biotoxicity of this type of drugs are still unclear, the data obtained evidence that the lipophilicity of metabolites may be a contributing factor for the qualitative differences found in their activity. In addition, the partition coefficients of the ionic drugs were calculated using three available software packages: ModesLab, Dragon, and HyperChem. As shown by cross-comparison of the experimental and calculated values, HyperChem was the most reliable software for achieving the main goal. The data obtained so far seem to be correlated to the proposed metabolic pathways of the drugs and could be of great value in understanding their pharmacological and/or toxicological profiles at the molecular level. This study may also contribute to gaining an insight into the mechanisms of biotransportation of this type of compounds given that the ionic partition coefficients reflect their ability to cross the membrane barriers.

Characterization of doping and electropolymerization of free standing films of polyterthiophene

To characterize the doping and electropolymerize a free-standing semiconducting polymer, the technique of electrodeposition at the Interface between Two Immiscible Electrolyte Solutions (ITIES) was used. The potential use of such films for photovoltaic applications led to a ‘plain’ terthiophene being chosen as the starting monomer in order to have a longer conjugation length. A new design of a 4-electrode cell allowed us to operate at a relatively high potential but where the potential is still low compared with a value that would damage the formed polymer. The doping level is investigated by both cyclic voltammetric and steady state techniques.

Investigation of the effects of metalloporphyrin species containing different substitutes on electron transfer at the liquid/liquid interface

Scanning electrochemical microscopy (SECM) technology has been used to investigate the kinetics of heterogeneous electron transfer (ET) as a function of driving force at the interface between two immiscible electrolyte solutions (ITIES). The ET between metalloporphyrin species containing different substitutes in nitrobenzene and other redox species in the aqueous phase was studied and the rate constants were also extracted from the dependence of the steady-state current at a micrometer-sized tip electrode on the distance between the tip and the phase boundary when compared with the theoretical working curves. Corresponding to the various metalloporphyrin substitutes, SECM was demonstrated to be a useful means to study the effect of molecular structure on the kinetics of heterogeneous ET.

Thin‐Layer Cyclic Voltammetric and Scanning Electrochemical Microscopic Study of Antioxidant Activity of Ascorbic Acid at Liquid/Liquid Interface

AbstractAn electron transfer reaction between ascorbic acid (H2A) in an aqueous solution and oxidizing agent in an organic solution immiscible with water has been studied by thin‐layer cyclic voltammetry (TLCV) for charge transfer at the interface between two immiscible electrolyte solutions (ITIES). As an antioxidant, H2A provide electrons through the aqueous/organic interface to reduce Fc+ and the procedure has been proved to be a one electron process again. In this work, the first combination of TLCV and scanning electrochemical microscopy (SECM) was achieved and showed a reasonable agreement between the results from the two different approaches. Otherwise, lower concentration ratios Kr of aqueous to organic reactants was adopted, which is given as evidence to the proposed procedure of Barker.

Selective transfer of Ag + at the water|1,2-dichloroethane interface facilitated by complex formation with a calixarene derivative

The facilitated transfer of silver, Ag +, has been studied at the Interface between Two Immiscible Electrolyte Solutions (ITIES). The transfer was achieved with the assistance of a calixarene-based silver ionophore. An investigation of the mechanistic details of the transfer was conducted using cyclic voltammetry at both micro and macro liquid|liquid interfaces. The mechanism was found to follow a Transfer by Interfacial Complexation (TIC)/Transfer by Organic phase Complexation (TOC) mechanism. The complex stoichiometry was found to shift from 1:1 to 1:2, metal:ligand, with increasing ionophore concentration. The logarithms of the complex association constants, log β 1 o and log β 2 o , were estimated at 12.4 and 14.5, respectively. The charge transfer current was also found to be limited by diffusion of the transferring species and was unchanged by the presence of a range of interferents. The system thus shows promise for selective analytical applications.

Simulations of the adsorption of ionic species at polarisable liquid∣liquid interfaces

The adsorption of ions at the interface between two immiscible electrolyte solutions (ITIES) is primarily controlled by the potential distribution across the interface, which in turn is influenced by the adsorption process. In the present paper, we simulate the effect of the adsorption of charged species on the charge distribution at the ITIES based on the classical description of the interface employing the Gouy–Chapman model. The inner layer is considered as a charged plane, where the ionic adsorption takes place. The potential at this plane is determined by the electro-neutrality condition. Various adsorption isotherms are considered, including potential dependent isotherms based on the Langmuir and Frumkin adsorption models. The potential distribution and the charge density profile are derived by solving the Poisson–Boltzman equation numerically. We show that the charge distribution in the interfacial region is significantly affected by the adsorption of ionic species. Under certain conditions, the adsorption results in a non-monotonic potential distribution with a potential trap at the interface.

Cyclic and pulse voltammetric study of dopamine at the interface between two immiscible electrolyte solutions

The detection of dopamine by differential pulse voltammetry (DPV) and square wave voltammetry (SWV) at the interface between two immiscible electrolyte solutions (ITIES) has been studied. Voltammetry at the liquid/liquid (water/1,2-dichloroethane) interface provides a simple method for overcoming the major problem associated with dopamine detection by voltammetry at solid electrodes: the co-existence of ascorbate at higher concentrations. Selectivity for dopamine was achieved by the use of dibenzo-18-crown-6 as an ionophore for the facilitated transfer voltammetry of protonated dopamine across the ITIES. Under these conditions, ascorbate is not transferred and hence does not interfere in the ion transfer current for dopamine. By use of DPV and SWV, the lowest concentration detectable can be lowered from ca. 0.1 mM (obtained with cyclic voltammetry) to 2 μM. Evaluation of the effect of some other physiologically important species (acetylcholine, sodium, potassium and ammonium ions) on the dopamine transfer voltammetry has been studied, indicating the need for improved ionophore designs in order to achieve practically useful selectivity.

Microelectrochemical Techniques for Probing Kinetics at Liquid/Liquid Interfaces

We provide an overview of recent advances in microelectrochemical approaches to investigate the kinetics of various physicochemical processes that occur at the interface between two immiscible electrolyte solutions (ITIES). To place the advances in context, background material on the structure of the ITIES, derived from both experimental studies and computer simulation, is also provided. The main focus of the article is micro-ITIES techniques, single droplet measurements, microelectrochemical measurements at expanding droplets (MEMED) and scanning electrochemical microscopy (SECM). Recent developments in a combined SECM-Langmuir trough technique for probing diffusion processes across Langmuir monolayers at the water/air (W/A) interface are also highlighted, by considering an organic monolayer at a water surface as a special case of a liquid/liquid interface.

Amperometric method for determining the degree of complexation of polyelectrolytes with cationic surfactants

The complexation of sodium polystyrene sulfonate with monovalent cationic surfactants at a microsized liquid/liquid interface has been studied using electrochemistry. The method is based on measurement of surfactant ion transfer across the interface between two immiscible electrolyte solutions (ITIES). The complexation of various cationic surfactants (alkylpyridinium- and trimethylammonium-) with oligosized polystyrene sulfonate was measured. Binding isotherms were used to determine the degree of binding as a function of the surfactant chain length and type of head group. It was found that the hydrophobicity of the surfactant was the predominant factor. The effect of the polyelectrolyte chain length on the binding mechanism was studied using cetylpyridinium chloride as a complexing agent. It was found that binding affinity, as well as cooperativity of the binding process, decreases with decreasing polyelectrolyte chain length. Thermodynamics of surfactant binding was measured using titration microcalorimetry. The thermodynamic data obtained show that the enthalpy of surfactant binding is not dependent on polymer chain length, but an increase in chain length makes the binding process entropically more favorable.

Evidence for a Diffuse Interfacial Region at the Dichloroethane/Water Interface

The 1,2-dichloroethane (DCE)/water interface is important because of its suitability as an electrochemical interface between two immiscible electrolyte solutions (ITIES). An issue of particular interest is whether the interfacial region is molecularly sharp or whether the interface is comprised of a diffuse mixed interfacial region. These studies using vibrational sum-frequency spectroscopy as a probe of the structure, orientation, and bonding of interfacial water show that the interface is molecularly disordered with properties similar to a mixed phase interfacial region. It does not have the characteristics of a sharp interface that have been shown to occur at other liquid/liquid interfaces such as CCl4/H2O and alkane/H2O.