0000000000004283
AUTHOR
José A. Manzanares
showing 70 related works from this author
Variation of the Fermi level and the electrostatic force of a metallic nanoparticle upon colliding with an electrode.
2017
When a metallic nanoparticle (NP) comes in close contact with an electrode, its Fermi level equilibrates with that of the electrode if their separation is less than the cut-off distance for electron tunnelling. In the absence of chemical reactions in solution, the charge on the metallic nanoparticle is constant outside this range before or after the collision. However, the double layer capacitances of both the electrode and the NP are influenced by each other, varying as the function of distance. Because the charge on the nanoparticle is constant, the outer potential of the metallic NP and hence its Fermi level varies as the capacitance changes. This effect is more pronounced for small part…
Modelling the transport of carbonic acid anions through anion-exchange membranes
2003
Electrodiffusion of carbonate and bicarbonate anions through anion-exchange membranes (AEM) is described on the basis of the Nernst � /Planck equations taking into account coupled hydrolysis reactions in the external diffusion boundary layers (DBLs) and internal pore solution. The model supposes local electroneutrality as well as chemical and thermodynamic equilibrium. The transport is considered in three layers being an anion exchange membrane and two adjoining diffusion layers. A mechanism of
Diffusion and Migration
2003
The sections in this article are Introduction Fundamental Concepts Diffusion–migration Flux Equations Poisson Equation and the LEN Assumption Continuity Equation Ohm's Law and Migrational Transport Numbers Diffusion-conduction Flux Equation Diffusion Boundary Layer Faraday's Law and Integral Transport Numbers Nernst Equation and Concentration Overpotential Steady State Current–voltage Curves of Systems with One Active Species Integration of the Transport Equations Solutions of Homovalent Ions, |zi | =z Binary Electrolyte Solutions Ternary Electrolyte Solutions. The Supporting Electrolyte Weak Binary Electrolyte Steady State Current–overpotential Curves in the Presence of Supporting Electrol…
Understanding Digestive Ripening of Ligand-Stabilized, Charged Metal Nanoparticles
2017
Most syntheses of thiolate-protected metal nanoparticles (NPs) include a thermochemical step in which the as-prepared, polydisperse NPs are transformed to a narrower size distribution in a poorly understood process known as digestive ripening (DR). Previous theoretical approaches considered either surface and electrostatic contributions or surface and ligand-binding contributions. We show that the three contributions are needed to obtain theoretical predictions in agreement with experimental observations. Although statistical thermodynamics does not clarify mechanistic details, it certainly provides valuable insights on the DR process. Remarkably, a relatively simple theory with no fitting …
Study of the effect of the membrane composition on ion transfer across a supported liquid membrane
2003
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…
The interplay between cooperativity and diversity in model threshold ensembles
2014
The interplay between cooperativity and diversity is crucial for biological ensembles because single molecule experiments show a significant degree of heterogeneity and also for artificial nanostructures because of the high individual variability characteristic of nanoscale units. We study the cross-effects between cooperativity and diversity in model threshold ensembles composed of individually different units that show a cooperative behaviour. The units are modelled as statistical distributions of parameters (the individual threshold potentials here) characterized by central and width distribution values. The simulations show that the interplay between cooperativity and diversity results …
Associative Memory Based on Double-Gating of Molecularly Linked Nanosystem Arrays: A Theoretical Scheme
2008
We discuss theoretically the properties of an associative memory (a system that can retrieve a stored pattern that is similar to the input pattern) based on the ideal conductive properties of a molecularly linked nanosystem array. Two schemes are considered for the memory based on the gate potential modulation of the drain-source current through the array. In the first scheme, the basic units of the electric circuit are nanosystems (e.g., nanoparticles) arranged in a series array. Each nanosystem is assumed to have two states of conductances, GM and Gm (GM ≫ Gm), that can be tuned externally by the gate and backgate potentials. The bit sequence associated with a given pattern is stored as t…
Counterion transport numbers of poly(acrylic acid)-grafted porous ion-exchange membranes as determined from current step measurements
1997
Abstract The effect of an electric current on the concentration polarization of the external bathing solutions and the permselectivity of poly(acrylic acid)-grafted porous ion-exchange membranes has been studied. The experimental approach is based on the transient behavior of the total electric potential drop through the membrane cell when a current step is imposed from external nonpolarizable electrodes. When this voltage drop is recorded as a function of time, a transition time characteristic of each membrane system is obtained. From this time, the counterion transport number for the salt solution (KClH2O) in the membrane can be obtained. The theoretical modeling is based on the time-dep…
Electrochemical impedance spectroscopy of polyelectrolyte multilayer modified gold electrodes: influence of supporting electrolyte and temperature.
2005
Electrochemical impedance spectroscopy and cyclic voltammetry are employed to characterize poly(styrenesulfonate)/poly(allylamine hydrochloride) multilayers assembled onto cysteamine-modified gold surfaces. The influence of the supporting electrolyte and temperature on the impedance response is studied because of both its practical interest and the need to test further the capillary membrane model recently developed by Barreira et al. [J. Phys. Chem. B 2004, 108, 17973]. The results obtained are interpreted quite satisfactorily in terms of this model, thus providing additional support to its usefulness for the description of ionic transport through polyelectrolyte multilayers. It is observe…
Modeling of surface vs. bulk ionic conductivity in fixed charge membranes
2003
A two-region model for describing the conductivity of porous fixed charge membranes is proposed. In the surface region, the conductivity is due to the mobile positive ions (counterions) around the negative fixed charges. In the pore center region, the conductive properties resemble those of the external electrolyte solution because the fixed charges are assumed to be effectively neutralized by the counterions in the surface region. Activation energies and surface diffusion coefficients are estimated by assuming that the counterion jump from a fixed charge group is the rate limiting process for surface transport. The barrier energy for this jump is calculated using a simple electrostatic mod…
Thermodynamic analysis of binding between drugs and glycosaminoglycans by isothermal titration calorimetry and fluorescence spectroscopy
2007
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
2018
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 …
Equilibrium swelling properties of polyampholytic hydrogels
1996
The role of counter ions and ion dissociation in establishing the equilibrium swelling of balanced and unbalanced polyampholytic hydrogels has been investigated experimentally and theoretically. The swelling dependence on both the net charge offset and the external bath salt concentration has been examined using an acrylamide based polyampholytic hydrogels. By careful consideration of the swelling kinetics, we illustrate the effects of ion dissociation equilibria and counter ion shielding in polyampholytic hydrogels near their balance point where both polyelectrolyte and polyampholyte effects are present. The theory considers a Flory type swelling model where the Coulombic interactions betw…
Donnan phenomena in membranes with charge due to ion adsorption. Effects of the interaction between adsorbed charged groups
1993
A physical model for the modified Donnan phenomenon associated with ion adsorption on localized membrane sites is presented. This model accounts for the dependence of the concentration of adsorbed ions on electrolyte concentration and pH as it is influenced by the electrostatic interaction between adsorbed ions. The equilibrium thermodynamic concepts employed are based on the Donnan formalism for the ion equilibria between membrane and solution, and the Bragg–Williams approximation for an adsorption isotherm that incorported interaction between adsorbed ions. Our results include the concentration of charged groups in the membrane, the pH of the membrane phase solution, and the Donnan potent…
Pore entrance effects on the electrical potential distribution in charged porous membranes and ion channels
2007
Abstract Models for the electrical potential distribution in the interfacial region between a fixed charge membrane and an electrolyte solution have traditionally employed the Donnan equilibrium formalism that assumes discontinuous changes in concentrations and electric potential. In the case of the charged capillary membrane model, we propose to check rigorously the validity of this approach by solving the linearized Poisson–Boltzmann equation for the diffuse electrical double layer at the membrane|solution interface. The comparison of the resulting axial distribution for the electric potential with the Donnan potential drop shows that the discontinuous approach is only valid for membrane …
Model for ion transport in bipolar membranes.
1990
A simple theory for multi-ionic transport, nonequilibrium water dissociation, and space-charge effects in bipolar membranes is developed on the basis of some of the concepts used in the solid-state n-p junction. Ion transport is described in terms of the Nernst-Planck flux equation and nonequilibrium water dissociation is accounted for by the Onsager theory of the second Wien effect. The model is expected to be of interest for biological and synthetic membranes, and can explain a number of observed effects.
Ion-exchange fibers and drugs: an equilibrium study
2001
The purpose of this study was to investigate the mechanisms of drug binding into and drug release from cation-exchange fibers in vitro under equilibrium conditions. Ion-exchange groups of the fibers were weakly drug binding carboxylic acid groups (-COOH), strongly drug binding sulphonic acid groups (-SO(3)H), or combinations thereof. Parameters determining the drug absorption and drug release properties of the fibers were: (i) the lipophilicity of the drug (tacrine and propranolol are lipophilic compounds, nadolol is a relatively hydrophilic molecule), (ii) the ion-exchange capacity of the fibers, which was increased by activating the cation-exchange groups with NaOH, (iii) the ionic streng…
Controlled transdermal iontophoresis by ion-exchange fiber
2000
The objective of this study was to assess the transdermal delivery of drugs using iontophoresis with cation- and anion-exchange fibers as controlled drug delivery vehicles. Complexation of charged model drugs with the ion-exchange fibers was studied as a method to achieve controlled transdermal drug delivery. Drug release from the cation-exchange fiber into a physiological saline was dependent on the lipophilicity of the drug. The release rates of lipophilic tacrine and propranolol were significantly slower than that of hydrophilic nadolol. Permeation of tacrine across the skin was directly related to the iontophoretic current density and drug concentration used. Anion-exchange fiber was te…
Biologically inspired information processing and synchronization in ensembles of non-identical threshold-potential nanostructures.
2013
Nanotechnology produces basic structures that show a significant variability in their individual physical properties. This experimental fact may constitute a serious limitation for most applications requiring nominally identical building blocks. On the other hand, biological diversity is found in most natural systems. We show that reliable information processing can be achieved with heterogeneous groups of non-identical nanostructures by using some conceptual schemes characteristic of biological networks (diversity, frequency-based signal processing, rate and rank order coding, and synchronization). To this end, we simulate the integrated response of an ensemble of single-electron transisto…
Surface charge regulation of functionalized conical nanopore conductance by divalent cations and anions
2019
Abstract The surface charge regulation in nanoscale volumes is a subject of wide interest to biological and chemical soft matter systems. Also, electrolyte mixtures with monovalent and divalent ions are commonplace in practical applications with micro and nanoporous ion-exchange membranes. We have studied experimentally and theoretically the conductance of conical nanopores functionalized with negative and positive surface charges that are bathed by electrolyte mixtures of the monovalent ions K+ and Cl− and the divalent ions Mg2+, Ba2+, Ca2+, and SO42−. Small concentrations of these ions can modulate the nanopore selectivity and conductance because of their interaction with the charged grou…
Preparation of nanostructures composed of dextran sulfate/ruthenium nanoparticles and their interaction with phospholipid monolayers at a liquid–liqu…
2007
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- …
Sub-threshold signal processing in arrays of non-identical nanostructures
2011
Weak input signals are routinely processed by molecular-scaled biological networks composed of non-identical units that operate correctly in a noisy environment. In order to show that artificial nanostructures can mimic this behavior, we explore theoretically noise-assisted signal processing in arrays of metallic nanoparticles functionalized with organic ligands that act as tunneling junctions connecting the nanoparticle to the external electrodes. The electronic transfer through the nanostructure is based on the Coulomb blockade and tunneling effects. Because of the fabrication uncertainties, these nanostructures are expected to show a high variability in their physical characteristics and…
Ion transport through polyelectrolyte multilayers under steady-state conditions
2004
Abstract The permeability of a self-assembled polyelectrolyte multilayer to small ions under the influence of an applied potential difference is studied as a function of the number of layers and the nature of the supporting electrolyte. The multilayer is described as a series of homogeneously charged membranes with alternating sign of their fixed charge. Ion transport is described on the basis of the diffusion equation and the assumption of (Donnan) electrochemical equilibrium at the boundaries between layers. The calculated steady-state current–voltage curves are found to be in good agreement with experimental linear sweep voltammograms (at low sweep rate). The permeability of polystyrenes…
Electrochemical Impedance Spectroscopy of Polyelectrolyte Multilayer Modified Electrodes
2004
Electrochemical impedance spectroscopy, Fourier transform infrared reflection−absorption spectroscopy, and cyclic voltammetry were employed to characterize polyelectrolyte multilayers (PEMs) fabricated with poly(styrenesulfonate) as the polyanion and the polypeptides poly-l-histidine, poly-l-lysine, and poly-l-arginine as polycations. The layer-by-layer electrostatic assembly was produced onto alkanethiol-modified gold surfaces. The frequency response reveals that the effect of the number of layers seems to be related to a progressive reduction in the active area of the PEM-modified electrodes. The active area after the deposition of seven layers can be lower than 10% of its original value.…
Convective mass transfer to partially recessed and porous electrodes
2003
Abstract The diffusional problem of a rotating porous electrode has been analysed based on the mass transfer equations for a partially blocked electrode. It is shown that the porous geometry leads to a dependence of the current on rotation rate identical to that corresponding to a coupled diffusion-activated electron transfer mechanism. The apparent rate constant, however, is related only to the geometry of the porous surface. It is shown that the characteristic diffusional length corresponds to the pore dimension modified by a term including the transition from linear to spherical diffusional geometry at the pore entrance. The theory is compared with experimental results for the reduction …
Nonlinear conductance and heterogeneity of voltage-gated ion channels allow defining electrical surface domains in cell membranes
2015
Abstract The membrane potential of a cell measured by typical electrophysiological methods is only an average magnitude and experimental techniques allowing a more detailed mapping of the cell surface have shown the existence of spatial domains with locally different electric potentials and currents. Electrical potentials in non-neural cells are regulated by the nonlinear conductance of membrane ion channels. Voltage-gated potassium channels participate in cell hyperpolarization/depolarization processes and control the electrical signals over the cell surface, constituting good candidates to study basic biological questions on a more simplified scale than the complex cell membrane. These ch…
Thermodiffusion of sodium polystyrene sulfonate in a supporting electrolyte
2019
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
1995
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 …
Reliable signal processing using parallel arrays of non-identical nanostructures and stochastic resonance
2010
In the stochastic resonance (SR) phenomena, the response of a non-linear system to a weak periodic input signal is optimised by the presence of a particular level of noise which enhances signal detection. We explore, theoretically, the influence of thermal noise in arrays of metal nanoparticles functionalised with organic ligands acting as tunnelling junctions, with emphasis on the interplay between the SR phenomena and the nanostructure variability. In this system, the transference of a reduced number of electrons may suffice to implement a variety of electronic functions. However, because nanostructures are expected to show a significant variability in their physical characteristics, it i…
Device variability and circuit redundancy in signal processing based on nanoswitches
2009
Signal processing based on molecular switches whose conductance can be tuned by an external stimulus between two (on and off) states has been proposed recently (Cervera et al 2008 J. Appl. Phys. 104 084317). The basic building block is a metal nanoparticle linked to two electrodes by an organic ligand and a nanoswitch. The net charge delivered by this nanostructure exhibits a sharp resonance when the alternating potential applied between the electrodes has the same frequency as the periodic variation between the on and off conductance states induced on the nanoswitch. This resonance can be used to process an external signal by selectively extracting the weight of the different harmonics. Ho…
Electrochemical Characterization of Polyelectrolyte/Gold Nanoparticle Multilayers Self-Assembled on Gold Electrodes
2006
Polyelectrolyte/gold nanoparticle multilayers composed of poly(l-lysine) (pLys) and mercaptosuccinic acid (MSA) stabilized gold nanoparticles (Au NPs) were built up using the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of MSA. The assemblies were characterized using UV-vis absorption spectroscopy, cyclic and square-wave voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy. Charge transport through the multilayer was studied experimentally as well as theoretically by using two different redox pairs [Fe(CN)(6)](3-/4-) and [Ru(NH(3))(6)](3+/2+). This paper reports a large sensitivity to the charge of the out…
Enhanced ion transfer rate due to the presence of zwitterionic phospholipid monolayers at the ITIES
2000
Abstract The transfer of cations across phospholipid monolayers at ITIES is studied both experimentally and theoretically. Further evidence of the enhanced rate for cation transfer due to the presence of the monolayer is presented, and a theoretical model that can explain these observations is worked out. The system considered experimentally is Li + ion transfer across a hemispherical water ∣ 1,2-dichloroethane interface covered by distearoyl phosphatidylcholine. The theoretical description is based on the electrical double layer correction to the Butler–Volmer equation, coupled with a solution of the Poisson–Boltzmann equation across the interfacial region. The phospholipid monolayer is mo…
Heat and work fluxes in thermoelectric coolers
2021
Abstract Thermodynamics considers heat and work as the observables of energy. Then, in a non-equilibrium process, the fluxes of heat, work and energy are related. The expressions for the heat and energy flux densities are well known; although several conventions have been adopted. The work flux density defined from the heat and energy flux densities can be very useful in describing the energy balance when chosen to emphasize observable quantities. This paper discusses the advantages of the use of the conduction heat flux density given by Fourier’s law and a work flux density defined from it. As a case study, heat and work fluxes are evaluated in the elements of a thermoelectric cooler using…
Determination of rate constants of ion transfer kinetics across immiscible electrolyte solutions
1998
Abstract The rotating diffusion cell was used to study ion transfer across the interface between two immiscible electrolyte solutions. Tetrabutylammonium was chosen as the transferring cation and lithium chloride as the supporting electrolyte in aqueous phase. Tetrabutylammonium tetrakis-(4-fluorophenyl)-borate in 2-nitrophenyl-octylether was used as the organic electrolyte solution supported in the porous membrane. The quasi-steady state current–voltage curves were measured both by applying potential steps and by imposing a slow potential sweep. The analysis of experimental results was based on the comparison with the theoretical current–voltage curves and on the Koutecky–Levich plots. The…
Noise assisted image processing by ensembles of R-SETs
2017
AbstractWe study how noise can assist the processing of an image in a resistance-single electron transistor (R-SET) model. The image is an 8-bit black and white picture. Every grey level is codified linearly into a sub-threshold input potential applied for a prescribed time window to an ensemble of R-SETs that transforms it into a spiking frequency. The addition of a background white noise potential of high amplitude permits the ensemble to process the image by means of the stochastic resonance phenomenon. Aside from the positive aspects, we analyse the negative impact of using noise and how we can minimize it using redundancy and a longer measuring time. The results are compared with the c…
Modified Donnan phenomena in polyaniline with poly(vinyl sulphonate) chains
1993
We develop a physical model, based on the modified Donnan phenomena ideas introduced previously by the authors, to describe the acid doping of the conducting polymer polyaniline. The theory is motivated by the experimental work of Asturias et al. [Ber. Bunsenges. Phys. Chem. 95, 1381 (1991)]. Good agreement between theory and experiment is found.
Electrical Coupling in Ensembles of Nonexcitable Cells: Modeling the Spatial Map of Single Cell Potentials
2015
We analyze the coupling of model nonexcitable (non-neural) cells assuming that the cell membrane potential is the basic individual property. We obtain this potential on the basis of the inward and outward rectifying voltage-gated channels characteristic of cell membranes. We concentrate on the electrical coupling of a cell ensemble rather than on the biochemical and mechanical characteristics of the individual cells, obtain the map of single cell potentials using simple assumptions, and suggest procedures to collectively modify this spatial map. The response of the cell ensemble to an external perturbation and the consequences of cell isolation, heterogeneity, and ensemble size are also ana…
Nanopore charge inversion and current-voltage curves in mixtures of asymmetric electrolytes
2018
[EN] We consider the screening of the negative charges (carboxylic acid groups) fixed on the surface of a conical-shaped track-etched nanopore by divalent magnesium (Mg2+) and trivalent lanthanum (La3+). The experimental current (I)-voltage (V) curves and current rectification ratios allow discussing fundamental questions about the overcompensation of spatially-fixed charges by multivalent ions over nanoscale volumes. The effects of charge inversion or reversal on nanopore transport are discussed in mixtures of asymmetric electrolytes (LaCl3 and MgCl2 with KCl). In particular, pore charge inversion is demonstrated for La3+ as well as for mixtures of this trivalent ion at low concentrations …
True and Apparent Oxygen Permeabilities of Contact Lenses
1992
We studied the passage of oxygen through some commercially available contact lenses. Oxygen diffusion coefficients were determined by the time-lag method and a 201T Redher permeometer was used to measure the oxygen permeability and transmissibility by the polarographic method. The measurements were carried out at room temperature with 0.09% sodium chloride physiologic solution. The following types of lenses were tested: (1) 12 lenses of cellulose acetate butyrate (CAB) of a mean thickness of 0.194 mm (observed Dk approximately 6.3 barrers) (1 barrier is equivalent to 10(-11) cm3 of O2 (STP).cm2/cm3.s.mm Hg). (2) 13 lenses of a cross-linked polyhydroxyethyl methacrylate (2-HEMA), manufacture…
Electrochemical study of copper chloride complexes in the RTIL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide
2013
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…
Interpretation of Ocular Melanin Drug Binding Assays. Alternatives to the Model of Multiple Classes of Independent Sites
2016
Melanin has a high binding affinity for a wide range of drugs. The determination of the melanin binding capacity and its binding affinity are important, e.g., in the determination of the ocular drug distribution, the prediction of drug effects in the eye, and the trans-scleral drug delivery. The binding parameters estimated from a given data set vary significantly when using different isotherms or different nonlinear fitting methods. In this work, the commonly used bi-Langmuir isotherm, which assumes two classes of independent sites, is confronted with the Sips isotherm. Direct, log-log, and Scatchard plots are used, and the interpretation of the binding curves in the latter is critically a…
Cooperative Effects Enhance Electric-Field-Induced Conductance Switching in Molecular Monolayers
2011
The anchoring of molecules with functional groups at surfaces permits information processing based on two stable molecular states that can be tuned externally by light irradiation and external fields. By using a molecular model that incorporates the essential characteristics of the problem, we show that the local interactions between adjacent molecules in a densely packed monolayer can stabilize domains with the same molecular state because of cooperative processes, enhancing significantly the switching properties between the molecular states. The case of electric-field-induced conductance switching is exploited in two possible applications: the design of a logic gates system and the operat…
Drug Distribution to Retinal Pigment Epithelium: Studies on Melanin Binding, Cellular Kinetics, and Single Photon Emission Computed Tomography/Comput…
2016
Melanin binding is known to affect the distribution and elimination of ocular drugs. The purpose of this study was to evaluate if the extent of drug uptake to primary retinal pigment epithelial (RPE) cells could be estimated based on in vitro binding studies with isolated melanin and evaluate the suitability of single photon emission computed tomography/computed tomography (SPECT/CT) in studying pigment binding in vivo with pigmented and albino rats. Binding of five compounds, basic molecules timolol, chloroquine, and nadolol and acidic molecules methotrexate and 5(6)-carboxy-2',7'-dichlorofluorescein (CDCF), was studied using isolated melanin from porcine choroid-RPE at pH 5.0 and 7.4. The…
Deviations from equilibrium at the interface of a charged membrane
1989
The local equilibrium assumption commonly employed for the transport through the interface of a charged membrane has been analysed from a simplified electric double layer model. This layer is characterized on the basis of a surface potential arising from a non-zero surface charge density placed on the membrane surface. The dependence of deviations from local equilibrium on the characteristic parameters of the problem is shown. Connection with the classical treatment by Donnan is discussed. Although the complexity of the problem calls for a number of simplifications, the results obtained appears to be significative. Thus, the analysis carried out displays not only that deviations from equili…
Distribution potential in electrified microemulsions with potential determining salts
2018
Abstract The electrical polarization of lamellar and water-in-oil microemulsions composed of the aqueous solution of a potential determining salt (PDS), an organic solvent and a nonionic surfactant has been studied. The distribution of the PDS ions across the interface between two immiscible electrolyte solutions (ITIES) generates an electrical potential difference which can be used to control charge transfer processes. In macroscopic ITIES, this distribution potential is independent of the PDS concentration and can be determined from the electroneutrality condition far from the interface. In microemulsions, on the contrary, the distribution potential is smaller in magnitude and depends on …
Polarity and bioelectrical patterning in a linear chain of non-excitable cells
2020
Abstract Polarity in multicellular systems is influenced by bioelectrical signals because electric potentials can act as spatio-temporal patterns for other biochemical processes that eventually emerge as long-lasting biological outcomes. We study the role of the electric potential in establishing head-tail polarity for the case of a chain of non-excitable cells. This biophysical model incorporates both single-cell (membrane ion channels) and multicellular (intercellular gap junctions) characteristics. The results are presented in the form of a bioelectrical phase space that complements traditional biochemical approaches and provides qualitative insights for the case of anterior/posterior po…
Thermodynamics of Rubber Elasticity
2001
A thermodynamic study of an isotropic rubber band under uniaxial stress is presented on the basis of its equation of state. The behavior of the rubber band is compared with both that of an ideal elastomer and that of an ideal gas, considering the generalized Joule's law as the ideality criterion.
Ion-exchange fibers and drugs: a transient study.
2003
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…
Observable Electric Potential and Electrostatic Potential in Electrochemical Systems
1999
The role of the electric potential in the description of transport processes in electrochemical systems is critically analyzed. Since the electrostatic potential drop between two parts of a system ...
Phospholipid monolayers at water∣oil interfaces: theoretical modelling of surface pressure–molecular area isotherms
1998
Abstract The phospholipid adsorption and surface pressure–molecular area isotherms at interfaces are interpreted theoretically from two-dimensional (2D) lattice and real gas models that incorporate a minimum number of adjustable parameters. The first model is based on the lattice statistics of binary solutions and the molecular parameters introduced are the energy changes involved in the mixing process of the phospholipid and organic solvent molecules and the effective phospholipid head area. The surface pressure is interpreted in terms of the difference between the two liquid surface tensions. The second model makes use of (i) a non-localised adsorption model with a square-well potential e…
Effects of a macroscopic fixed charge inhomogeneity on some membrane transport properties
1991
Abstract The effects that a macroscopic fixed charge inhomogeneity exerts on some membrane transport properties have been theoretically analyzed. To this end, we introduce two particular inhomogeneous fixed charge distributions on the basis of previous experimental work, and the transport equations are assumed to be the Nernst-Planck equations. It is found that a macroscopic redistribution of a constant quantity of fixed charge groups can modify the observed transport properties, the two inhomogeneous membranes here considered exhibiting permselectivities different from those of otherwise identical homogeneous membranes. Although the main emphasis of the study is on the basic aspects of tra…
How does a transition zone affect the electric field enhanced water dissociation in bipolar membranes?
1994
The changes in the electric field in the space charge regions and the corresponding effect on the water dissociation rate when a transition zone exists between the layers of a bipolar membrane are theoretically studied. A quasi-equilibrium approach based on the Poisson-Boltzmann equation for the space charge interfacial regions is used. The transition zone acts to decrease significantly the water dissociation rate. However, for realistic values of the thickness δ of the transition zone and provided that the ohmic drop over δ be small, this decrease in the dissociation rate is not very dependent on δ. The results obtained give theoretical support to some recent experimental findings.
Weakly coupled map lattice models for multicellular patterning and collective normalization of abnormal single-cell states
2017
We present a weakly coupled map lattice model for patterning that explores the effects exerted by weakening the local dynamic rules on model biological and artificial networks composed of two-state building blocks (cells). To this end, we use two cellular automata models based on: (i) a smooth majority rule (model I) and (ii) a set of rules similar to those of Conway's Game of Life (model II). The normal and abnormal cell states evolve according with local rules that are modulated by a parameter $\kappa$. This parameter quantifies the effective weakening of the prescribed rules due to the limited coupling of each cell to its neighborhood and can be experimentally controlled by appropriate e…
Double layer potential and degree of dissociation in charged lipid monolayers
2000
Abstract One of the contributions to the surface potential in charged phospholipid monolayers at air–water interfaces is the double layer potential. In this note several misconceptions found in the literature concerning the relationship between the double layer potential and the degree of dissociation of the lipid polar headgroups are critically analyzed. The deviations of the double layer potential measurements from the Gouy–Chapman theory observed by several authors are explained by taking into account the dependence of the degree of dissociation with concentration, area per lipid molecule and pH.
Contact Potentials, Fermi Level Equilibration, and Surface Charging.
2016
This article focuses on contact electrification from thermodynamic equilibration of the electrochemical potential of the electrons of two conductors upon contact. The contact potential difference generated in bimetallic macro- and nanosystems, the Fermi level after the contact, and the amount and location of the charge transferred from one metal to the other are discussed. The three geometries considered are spheres in contact, Janus particles, and core-shell particles. In addition, the force between the two spheres in contact with each other is calculated and is found to be attractive. A simple electrostatic model for calculating charge distribution and potential profiles in both vacuum an…
Analysis of adsorption of phospholipids at the 1,2-dichloroethane/water interface by electrochemical impedance spectroscopy: A study of the effect of…
2007
Abstract The adsorption behaviour of a series of phosphatidylcholines (PCs) with saturated carbon chains of different length (DLPC, DPPC, DSPC, DAPC, and DBPC) at the electrified 1,2-dichloroethane/water interface was studied by measuring electrochemical impedance spectroscopy at the polarized interface. Two different trends in the interfacial capacitance were observed for any of the PCs the capacity dependence on the applied potential: strong adsorption occurs at negative potential with a marked decrease of C ( E ); increase of capacity is observed at positive potentials. It is demonstrated that the interfacial lipid adsorption was dependent on phospholipid concentration, applied potential…
Correction: Variation of the Fermi level and the electrostatic force of a metallic nanoparticle upon colliding with an electrode.
2017
The nanoparticle potential varies with the distance from the electrode, and sometimes like attracts like.
Configurational entropy of microemulsions : The fundamental length scale
1993
Phenomenological models have been quite successful in characterizing both the various complex phases and the corresponding phase diagrams of microemulsions. In some approaches, e.g., the random mixing model (RMM), the lattice parameter is of the order of the dimension of an oil or water domain and has been used as a length scale for computing a configurational entropy, the so‐called entropy of mixing, of the microemulsion. In the central and material section of this paper (Sec. III), we show that the fundamental length scale for the calculation of the entropy of mixing is of the order of the cube root of the volume per molecule—orders of magnitude smaller than the dimension of such a domain…
Electrochemically Controlled Ion Dynamics in Porphyrin Nanostructures
2020
peer-reviewed The full text of this article will not be available in ULIR until the embargo expires on the 22/07/2021 The dynamics of ion intercalation into solid matrices influences the performance of key components in most energy storage devices (Li-ion batteries, supercapacitors, fuel cells, etc.). Electrochemical methods provide key information on the thermodynamics and kinetics of these ion-transfer processes but are restricted to matrices supported on electronically conductive substrates. In this article, the electrified liquid|liquid interface is introduced as an ideal platform to probe the thermodynamics and kinetics of reversible ion intercalation with nonelectronically active matr…
Thermodynamics based on the principle of least abbreviated action: Entropy production in a network of coupled oscillators
2006
We present some novel thermodynamic ideas based on the Maupertuis principle. By considering Hamiltonians written in terms of appropriate action-angle variables we show that thermal states can be characterized by the action variables and by their evolution in time when the system is nonintegrable. We propose dynamical definitions for the equilibrium temperature and entropy as well as an expression for the nonequilibrium entropy valid for isolated systems with many degrees of freedom. This entropy is shown to increase in the relaxation to equilibrium of macroscopic systems with short-range interactions, which constitutes a dynamical justification of the Second Law of Thermodynamics. Several e…
Scanning electrochemical microscopy as a probe of Ag+ binding kinetics at Langmuir phospholipid monolayers
2005
A new method has been developed for measuring local adsorption rates of metal ions at interfaces based on scanning electrochemical microscopy (SECM). The technique is illustrated with the example of Ag+ binding at Langmuir phospholipid monolayers formed at the water/air interface. Specifically, an inverted 25 microm diameter silver disc ultramicroelectrode (UME) was positioned in the subphase of a Langmuir trough, close to a dipalmitoyl phosphatidic acid (DPPA) monolayer, and used to generate Ag+ via Ag electro-oxidation. The method involved measuring the transient current-time response at the UME when the electrode was switched to a potential to electrogenerate Ag+. Since the Ag+/Ag couple…
Convective electrodiffusion processes through graft-modified charged porous membranes
1999
Convective diffusion and electrophoresis across a charged porous membrane showing variable permeability properties were studied. The membrane used was prepared by grafting poly(acrylic acid) (PAA) onto a porous polyvinylidene fluoride (PVDF) membrane. The degree of grafting was selected to be relatively low, 18 wt%, to compromise between the ion selectivity and hydraulic permeability of the membrane. The possible electric field induced effects on the membrane permselectivity were examined after the membrane had been characterized by convective diffusion and concentration cell potential measurements. The measured electrophoresis data, however, could be modelled using the extended Teorell–Mey…
Space charge effect on competitive ion transport through ion-exchange membranes
2002
A mathematical model of the competitive electro-transport of two counter-ions through an ion exchange membrane based on the Nernst-Planck and Poisson equations is developed. A three-layer system is considered: the membrane and two adjacent diffusion layers. Concentration profiles in the three layers, effective transport numbers as functions of the current and current-voltage characteristics are calculated. Deviation from the local electroneutrality in space charge region near the depleted solution/membrane interface is taken into account. It is shown that the space charge region grows with the voltage applied. However the fluxes of the competitive counter-ions at over-limiting currents are …
Thermal potential of ion-exchange membranes and its application to thermoelectric power generation
2016
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 …
Effect of self-assembled surfactant structures on ion transport across the liquid|liquid interface
1999
In this paper, the effect of a coadsorbed polyanion–cationic surfactant system on the transport of tetraethylammonium ion across the water|1,2-dichloroethane interface is studied. It is shown that the change in double-layer structure due to the presence of adsorbed or coadsorbed surfactant can explain the experimental observations, thus concluding that no other effects on ion transfer (e.g., steric hindrance) are relevant under these experimental conditions. The implications of these results are discussed. Keywords: ITIES, Ion transfer, Self-assembled monolayers, Surfactants, Double-layer effects
Cell-cell bioelectrical interactions and local heterogeneities in genetic networks: a model for the stabilization of single-cell states and multicell…
2018
Genetic networks operate in the presence of local heterogeneities in single-cell transcription and translation rates. Bioelectrical networks and spatio-temporal maps of cell electric potentials can influence multicellular ensembles. Could cell-cell bioelectrical interactions mediated by intercellular gap junctions contribute to the stabilization of multicellular states against local genetic heterogeneities? We theoretically analyze this question on the basis of two well-established experimental facts: (i) the membrane potential is a reliable read-out of the single-cell electrical state and (ii) when the cells are coupled together, their individual cell potentials can be influenced by ensemb…
Synchronization of Bioelectric Oscillations in Networks of Nonexcitable Cells: From Single-Cell to Multicellular States.
2019
Biological networks use collective oscillations for information processing tasks. In particular, oscillatory membrane potentials have been observed in nonexcitable cells and bacterial communities where specific ion channel proteins contribute to the bioelectric coordination of large populations. We aim at describing theoretically the oscillatory spatiotemporal patterns that emerge at the multicellular level from the single-cell bioelectric dynamics. To this end, we focus on two key questions: (i) What single-cell properties are relevant to multicellular behavior? (ii) What properties defined at the multicellular level can allow an external control of the bioelectric dynamics? In particular,…
Channel flow at an immobilised liquid|liquid interface
2000
A novel rectangular channel flow electrochemical cell for the study of liquid | liquid interfaces is presented. The organic phase is immobilised by the use of a gelling agent, while the aqueous phase flows past the interface. This creates an asymmetric setup that allows us to establish diagnostic criteria to determine, for example, the direction of the ion transfer. The effects of varying flow rate and sweep rate have been considered both theoretically and experimentally. By comparison with two-dimensional simulations, it is demonstrated that a simple one-dimensional theory can be used to describe the cyclic voltammetry response of the channel flow cell.
Synchronization of coupled single-electron circuits based on nanoparticles and tunneling junctions
2009
We explore theoretically the synchronization properties of a device composed of coupled single-electron circuits whose building blocks are nanoparticles interconnected with tunneling junctions. Elementary nanoscillators can be achieved by a single-electron tunneling cell where the relaxation oscillation is induced by the tunneling. We develop a model to describe the synchronization of the nanoscillators and present sample calculations to demonstrate that the idea is feasible and could readily find applications. Instead of considering a particular system, we analyze the general properties of the device making use of an ideal model that emphasizes the essential characteristics of the concept.…
Potential determining salts in microemulsions: interfacial distribution and effect on the phase behavior.
2013
In this work we consider potential determining salts, also referred to as phase transfer agents for a future objective of electrochemistry at the oil-water interface in microemulsions. We have studied these salts, composed of a hydrophilic and a hydrophobic ion, in microemulsion stabilized by nonionic surfactants with an oligo ethylene oxide headgroup. NMR measurements show that the salts preferentially dissociate across the surfactant interface between the oil and water domains, and hence create a potential drop across the surfactant film, and back to back diffuse double layers in the oil and water phases. These observations are also supported by Poisson-Boltzmann calculations. This adsorp…