Biomedical subjects

Ivo Nischang

Publications and source records attributed to Ivo Nischang.

5 recordsLinked to original sources

PubMed2006

Key to analyte migration and retention in electrochromatography.

This work identifies electrical field-induced concentration polarization (CP) as a key physical mechanism influencing the retention behavior of charged analytes in electrochromatography with fixed beds of porous adsorbent particles. Due to an insufficient screening of intraparticle surface charge, under most general conditions the porous (permeable) particles become charge-selective. CP is caused by coupled mass and charge transport normal to the charge-selective external surface of the permeable particles, which leads to concentration gradients of ionic species in the adjoining interparticle electrolyte solution. Cation-exchange (cation-selective) particles were employed to investigate the influence of applied voltage on the retention factor of counterionic, i.e., positively charged, analytes. It is demonstrated by macroscopic retention data and microscopic studies resolving the CP phenomenon on a particle scale that the dependence of CP on electrical field and mobile-phase ionic strengths is directly reflected in concomitant changes of analyte retention. The CP zones that develop at the interface between interparticle and intraparticle pore space are recognized by charged, but not electroneutral analytes while entering or leaving the particles. The intensity of these convective-diffusion boundary layers (CP zones) depends on the applied field strength and charge selectivity of a particle. Thus, it is the charge-selective transport between the interparticle and intraparticle pore space in packed beds that prevails under typical experimental conditions in electrochromatography and that forms the physical basis for a general electrical field dependence of the retention factor of charged analytes.

Journal Article↗

PubMed2006

Electrohydrodynamics in hierarchically structured monolithic and particulate fixed beds.

We have investigated the basic dependence of electroosmotic flow (EOF) velocity and hydrodynamic dispersion in capillary electrochromatography (CEC) on the variation of applied field and mobile phase ionic strengths employing silica-based particulate and monolithic fixed beds. These porous media have a hierarchical structure characterized by discrete intraparticle (intraskeleton) mesoporous and interparticle (interskeleton) macroporous spatial domains. While the macroporous domains contain quasi-electroneutral electrolyte solution, the ion-permselectivity (charge-selectivity) of the mesoporous domains determines the co-ion exclusion and counter-ion enrichment at electrochemical equilibrium (without superimposed electrical field) which depends on mesopore-scale electrical double layer (EDL) overlap and surface charge density. This adjustable, locally charge-selective transport realized under most general conditions forms the basis for concentration polarization (CP) induced by electrical fields superimposed in CEC. CP characterizes the formation of convective diffusion boundary layers with reduced (depleted CP zone) and increased (enriched CP zone) electrolyte concentration, respectively, at the anodic and cathodic interfaces in fixed beds containing the cation-selective, silica-based particles (or monolith skeleton). CP originates in the electrical field-induced coupled mass and charge transport normal to the charge-selective interfaces and has consequences for the EOF dynamics, hydrodynamic dispersion, and analyte retention in CEC. A secondary EDL with mobile counter-ionic space charge can be induced in the depleted CP zone leading to induced-charge EOF in the macroporous domains. It is characterized by a nonlinear dependence of the average EOF velocities on applied field strength and strong local velocity components tangential to the surface which enhance lateral pore-scale dispersion, thereby decreasing (axial) zone spreading. Differences in the pore space morphology of random-close sphere packings and monoliths criticially affect the intensity of CP and induced-charge EOF in these materials. CP is identified as a key phenomenon in CEC which also influences effective migration and the retention of charged analytes because the local intensity of CP inherently depends on applied field and mobile phase ionic strengths.

Chromatography, Liquid↗

PubMed2005

Perspective on concentration polarization effects in electrochromatographic separations.

This work illustrates the appearance and electrohydrodynamic consequences of concentration polarization in the particulate and monolithic fixed beds used in capillary electrochromatography and related electrical-field assisted processes. Key property of most porous materials is the co-existence of bulk, quasi-electroneutral macroporous regions and mesoporous compartments which are ion-permselective (due to electrical double-layer overlap) causing different transport numbers for co-ionic and counterionic species, e.g., background electrolyte components, or the analytes. For a cathodic electroosmotic flow the (cation) permselectivity, together with diffusive and electrokinetic transport induces depleted and enriched concentration polarization zones at the anodic and cathodic interfaces, respectively, in dependence of the mobile phase ionic strength and applied electrical fields. At high field strength a secondary, nonequilibrium electrical double layer may be created in the depleted concentration polarization zones of a material stimulating electroosmosis of the second kind. The potential of this induced-charge electroosmosis with respect to nonlinear flow velocities and electrokinetic instability mixing (basically destroying the concentration polarization zones) is analyzed in view of the pore space morphology in random-close packings of spherical-shaped, porous particles and hierarchically structured monoliths. Possible applications based on a fine-tuning of the illustrated effects emerge for microfluidic pumping and mixing, or the intensification of sample recovery in adsorption processes. With this perspective we want to focus the attention on concentration polarization in electrochromatographic systems by presenting and discussing original data acquired on relevant microscopic as well as macroscopic scales, and point towards the importance of related effects in colloid and membrane science.*

Chromatography↗

PubMed2004

Nonlinear electroosmosis in hierarchical monolithic structures.

We studied the dependence of electroosmotic flow (EOF) velocity and separation efficiency for neutral analytes in 100 microm ID capillary monoliths on a variation of the mobile phase ionic strength and applied electrical field strength, i.e., we covered a range for the concentration of Tris buffer from 10(-5) to 10(-2) M and applied electrical field strengths up to 10(5) V/m. The silica-based monoliths are hierarchically structured having intraskeleton mesopores and interskeleton macropores. While a linear dependence of the average EOF velocity on applied field strength could be observed with 5 x 10(-3) M Tris (turning slightly nonlinear at a higher concentration due to thermal effects), this dependence becomes systematically nonlinear as the Tris concentration is reduced towards 10(-4) M. Increased velocities by more than 50% compared to those expected from linear behavior are realized at 10(5) V/m. Concomitantly, as the Tris concentration is reduced from 10(-3) to 10(-4) M, we notice an improvement in plate heights by a factor of more than 2 (they approach 2 microm for ethylbenzoate). We complementary analyzed the onset of the nonlinear EOF dynamics in a hierarchical monolith and the significantly reduced axial dispersion in view of nonequilibrium electrokinetic effects which may develop in porous media due to the presence of ion-permselective regions, e.g., the mesoporous monolith skeleton. In this respect, a decreasing mobile phase ionic strength favors the formation of nonequilibrium concentration polarization in strong electrical fields, and a coupling of the electrostatics and hydrodynamics then may explain nonlinear EOF velocities and increasing separation efficiencies depending on the Tris concentration and applied field strength.

Capillary Action↗

PubMed2002

Deviceless decoupled electrochemical detection of catecholamines in capillary electrophoresis using gold microband array electrodes.

Samples containing microM concentrations of dopamine, (+/-)-isoproterenol, para-aminophenol and chlorogenic acid have been separated by capillary electrophoresis (CE) and detected using end-column amperometric detection based on a novel decoupling method. The present decoupling approach involves the use of an electrochemical detector chip containing an array of microband electrodes where the working and reference electrodes are positioned only 10 microm from each other. The short distance between the working and reference electrodes ensures that both electrodes are very similarly affected by the presence of the CE electric field. With this method, no shift in the detection potential was seen when the CE high voltage was applied. This eliminated the need for a reoptimization of the detection potential to compensate for the influence of the separation voltage on the detection. It is also demonstrated that catecholamines can be detected using gold microband electrodes by careful adjustment of the detection potential to avoid the formation of gold oxide. Such careful adjustments of the detection potential are straightforward using the present decoupling method.

Aminophenols↗