- B. Belt-Gritter van de (1)
- H.J. Busscher (1)
- J.F.L. Duval (3)
- H.P. Leeuwen van (1)
- H.C. Mei van der (1)
Rates of ionic reactions with charged nanoparticles in aqueous media
Duval, J.F.L. ; Leeuwen, H.P. van - \ 2012
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment, & General Theory 116 (2012)25. - ISSN 1089-5639 - p. 6443 - 6451.
diffusion-controlled reactions - streaming current - particles - electrokinetics - coagulation - complexes - films
A theory is developed to evaluate the electrostatic correction for the rate of reaction between a small ion and a charged ligand nanoparticle. The particle is assumed to generally consist of an impermeable core and a shell permeable to water and ions. A derivation is proposed for the ion diffusion flux that includes the impact of the equilibrium electrostatic field distribution within and around the shell of the particle. The contribution of the extra- and intraparticulate field is rationalized in terms of a conductive diffusion factor, fel, that includes the details of the particle geometry (core size and shell thickness), the volume charge density in the shell, and the parameters defining the electrostatic state of the particle core surface. The numerical evaluation of fel, based on the nonlinear Poisson–Boltzmann equation, is successfully complemented with semianalytical expressions valid under the Debye–Hückel condition in the limits of strong and weak electrostatic screening. The latter limit correctly includes the original result obtained by Debye in his 1942 seminal paper about the effect of electrostatics on the rate of collision between two ions. The significant acceleration and/or retardation possibly experienced by a metal ion diffusing across a soft reactive particle/solution interphase is highlighted by exploring the dependence of fel on electrolyte concentration, particle size, particle charge, and particle type (i.e., hard, core/shell, and entirely porous particles).
Coupling between electroosmotically driven flow and bipolar faradaic depolarization processes in electron-conducting microchannels
Qian, S.Z. ; Duval, J.F.L. - \ 2006
Journal of Colloid and Interface Science 297 (2006)1. - ISSN 0021-9797 - p. 341 - 352.
amphifunctionally electrified interfaces - metal/electrolyte solution interface - spherical ultramicroelectrodes - electrochemical-behavior - surface - electrokinetics - challenges - field - elctroosmosis - opportunities
A quantitative theory is proposed for the analysis of steady electroosmotically driven flows within conducting cylindrical microchannels. Beyond a threshold value of the electric field applied in the electrolyte Solution and parallel to the conducting surface, electrochemical oxidation and reduction reactions take place at the two extremities of the substrate. The spatial distribution of the corresponding local faradaic currents along the bipolar electrode is intrinsically coupled to that of the electric field in solution. The nonuniform distribution of the electric field alters the double layer composition, and in particular the zeta-potential Value, along the conducting Surface via the occurrence of concomitant electronic and ionic double layer charging processes. The combined spatial dependencies of the lateral electric field and electrokinetic potential considerably affects the distribution of the electroosmotic velocity field in the directions parallel and perpendicular to the surface depolarized by faradaic processes. In this paper, the coupling between bipolar electrodic behavior and electroosmoosis is explicitly investigated for the case of irreversible-that is, kinetically controlled-electron transfer reactions. Typical simulation results are presented and illustrate the possibility of controlling and optimizing electroosmotic flows in conducting channels by electrochemical means.
Analysis of the interfacial properties of fibrillated and nonfibrillated oral streptococcal strains from electrophoretic mobility and titration measurements : Evidence for the shortcomings of the classical soft-particle approach
Duval, J.F.L. ; Busscher, H.J. ; Belt-Gritter, B. van de; Mei, H.C. van der; Norde, W. - \ 2005
Langmuir 21 (2005)24. - ISSN 0743-7463 - p. 11268 - 11282.
atomic-force microscopy - colloidal particles - cell-wall - surface characteristics - protein antigens - network method - salivarius - electrokinetics - suspensions - recognition
Chemical and structural intricacies of bacterial cells complicate the quantitative evaluation of the physicochemical properties pertaining to the cell surface. The presence of various types of cell surface appendages has a large impact on those properties and therefore on various interfacial phenomena, such as aggregation and adhesion. In this paper, an advanced analysis of the electrophoretic mobilities of fibrillated and nonfibrillated strains (Streptococcus salivarius HB and Streptococcus salivarius HB-C12, respectively) is performed over a wide range of pH and ionic strength conditions on the basis of a recent electrokinetic theory for soft particles. The latter extends the approximate formalism originally developed by Ohshima by solving rigorously the fundamental electrokinetic equations without restrictions on the bacterial size, charge, and double layer thickness. It further allows (i) a straightforward implementation of the dissociation characteristics, as evaluated from titration experiments, of the ionogenic charged groups distributed throughout the bacterial cell wall and/or the surrounding exopolymer layer and (ii) the inclusion of possible specific interactions between the charged groups and ions from the background electrolyte other than charge-determining ions. The theory also enables an estimation of possible swelling/shrinking processes operating on the outer polymeric layer of the bacterium. Application of the electrokinetic model to HB and HB-C12 clearly shows a significant discrepancy between the amount of surface charges probed by electrophoresis and by protolytic titration. This is ascribed to the specific adsorption of cations onto pristine charged sites in the cell wall. Physicochemical parameters pertaining to the hydrodynamics (softness degree) and electrostatics of the bacterial cell wall (HB-C12) and soft polymeric layer (HB) are quantitatively derived