Search results for "Electrokinetic phenomena"
showing 10 items of 38 documents
Capillary electrokinetic fractionation mass spectrometry (CEkF/MS): Technology setup and application to metabolite fractionation from complex samples…
2014
Capillary electrokinetic fractionation (CEkF) is investigated as a new, simple, and robust approach for semipreparative and analytical sample analysis based on pKa -dependant pH-driven electrophoretic mobility. CEkF was optimized with contactless conductivity detection and conducted with 10 kV reverse voltage for 10 min, then coupled on/at-line to ESI/MS. We propose a semi-empirical model with 14 representative compounds based on the correlation between sample/medium pH regulating the partial charge, the electrokinetic loading of the capillary and intensity (I) of analytes. According to the model, an empirical function (I = f (pH)) could be derived to calculate the acid dissociation constan…
Multivariate optimization approach for chiral resolution of drugs using human serum albumin in affinity electrokinetic chromatography-partial filling…
2005
The enantiomeric resolution of chiral compounds using HSA by means of affinity EKC (AEKC)-partial filling technique is the result of a delicate balance between different experimental variables such as protein concentration, running pH (background electrophoretic buffer, protein and compound solutions) and protein solution plug length. In this paper multivariate optimization approaches for chiral separation of four basic drugs (alprenolol, oxprenolol, promethazine and propranolol) using HSA as chiral selector in AEKC-partial filling technique are studied. The experimental conditions to achieve maximum resolution are optimized using the Box-Behnken experimental design. Partial least squares a…
Zeta-Potential Study of Calcium Silicate Hydrates Interacting with Alkaline Cations
2001
An investigation into the interaction between alkaline cations and calcium silicate hydrates (CSH) was conducted by electrokinetic measurements, which provided information on the nature of the interface between the solid and its equilibrium solution. Calcium constitutes for the CSH surface a potential-determining cation. A model of the CSH surface could be proposed, accounting for the experimental evolution of the CSH zeta potential. The necessity of studying the zeta-potential evolution of the system as a function of the calcium activity, instead of its concentration, was underlined. The results obtained suggest a specific interaction between cesium and the CSH surface, whereas sodium and …
Electrochemical Interfaces: At the Border Line
2002
The sections in this article are Introduction Basic Concepts Thermodynamics of Electrified Interfaces Classical Models of Electrified Interfaces Helmholtz Model Gouy–Chapman–Stern–Grahame Model Diffuse and Compact Layer Properties Grahame Model in Comparison with Capacitance Data for Liquid Electrodes Compact Layer Properties Manifestations of the Diffuse Layer in Kinetics of Electrode Reactions Electrokinetic Phenomena Solid Electrodes: Effects of Polycrystallinity and Surface Roughness “Uniform” Model of Solid Electrodes. Surface Roughness Crystallographic Inhomogeneity Effects for Solid Electrode Surfaces EDL Structure for NonUniform Electrode Surfaces Surface Roughness Effect on the Dif…
Highly efficient separation of amines by electrokinetic chromatography using resorcarene-octacarboxylic acids as pseudo-stationary phases
1998
Abstract Resorcarene-octacarboxylic acids, macrocyclic molecules built up by four alkylidene-bridged resorcinol units, were synthesized and used as pseudostationary phases in electrokinetic chromatography (EKC). Resorcarenes provide a stable structure and good solubility in electrolytes even with organic modifiers. The high electrophoretic mobility of the resorcarene-octacarboxylic acids introduced here as pseudostationary phases is based on the eight partly deprotonated carboxylic groups. This offers a broad migration time window, which is the main parameter for the resolution of peaks. From three compounds with different alkyl chain lengths (C 1 , C 5 , C 11 ), the C 11 -resorcarene-octa-…
Electrokinetic Properties which Control the Coagulation of Silicate Cement Suspensions during Early Age Hydration
1998
The coagulation of cement particles during early age hydration has been previously identified as the first step of the setting and hardening of cement pastes. By hydrating Ca3SiO5and a silicate-rich clinker under controlled conditions, a correlation between the coagulation of the suspensions and the electrokinetic properties of particles is established. The zeta potential, and hence the surface charge, of particles in suspension depends on the calcium content of the medium. At low concentrations of Ca2+, the zeta potential of Ca3SiO5particles, calcium silicate hydrate (C–S–H), and clinker is negative (<−30 mV) and the suspensions are well dispersed. A strong coagulation occurs at intermedia…
Intrinsic Acidity of Surface Sites in Calcium Silicate Hydrates and Its Implication to Their Electrokinetic Properties
2014
Calcium Silicate Hydrates (C–S–H) are the major hydration products of portland cement paste. The accurate description of acid–base reactions at the surface of C–S–H particles is essential for both understanding the ion sorption equilibrium in cement and prediction of mechanical properties of the hardened cement paste. Ab initio molecular dynamics simulations at the density functional level of theory were applied to calculate intrinsic acidity constants (pKa’s) of the relevant ≡SiOH and ≡CaOH2 groups on the C–S–H surfaces using a thermodynamic integration technique. Ion sorption equilibrium in C–S–H was modeled applying ab initio calculated pKa’s in titrating Grand Canonical Monte Carlo simu…
Gibbs' Dividing Surface between a Fixed-Charge Membrane and an Electrolyte Solution. Application to Electrokinetic Phenomena in Charged Pores
1999
The Gibbs model for the boundary between two phases consists of replacing the finite interfacial region, where the properties of the system change gradually, by a dividing surface which acts as a third phase of zero volume in which some magnitudes change abruptly. This thermodynamic concept was recently applied to a planar interface between a fixed charge membrane and an electrolyte solution.1 The continuous decrease of counterions with the distance from the charged surface is replaced by a step function, so that the diffuse double layer is ideally represented by a charged region depleted of all co-ions. Here the cylindrical geometry is analyzed, and the planar case is revisited by proposin…
Enantiomeric separation of chiral phenoxy acid herbicides by electrokinetic chromatography. Application to the determination of analyte-selector appa…
2001
The enantiomeric resolution of chiral phenoxy acid herbicides was performed by electrokinetic chromatography using a cyclodextrin as chiral pseudophase (CD-EKC). A systematic evaluation of several neutral and charged cyclodextrins was made. Among the cyclodextrins tested, (2-hydroxy)propyl beta-cyclodextrin (HP-beta-CD) was found to be the most appropriate for the enantioseparation of phenoxy acids. The influence of some experimental conditions, such as nature and pH of the background electrolyte, chiral selector concentration, and temperature, on the enantiomeric separation of phenoxy acids was also studied. The use of a 50 mM electrolyte solution in ammonium formate at pH 5 and a temperat…
Fast enantiomeric separation of uniconazole and diniconazole by electrokinetic chromatography using an anionic cyclodextrin: application to the deter…
2000
The enantiomeric resolution of the fungicides uniconazole and diniconazole was performed using electrokinetic chromatography with cyclodextrins as pseudostationary phase (CD-EKC). A systematic evaluation of several chiral selectors was made. The anionic derivative carboxymethylated-gamma-cyclodextrin (CM-gamma-CD) was found to be the most appropriate for the enantioseparation of fungicides among all cyclodextrins tested. The influence of some experimental conditions such as nature and buffer pH, chiral selector concentration, and temperature on the enantiomeric separation of the compounds studied was also investigated. The use of a 50 mM phosphate buffer (pH 6.5) containing 5 mM CM-gamma-CD…