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Biomedical subjects

Vlastimil Hruska

Publications and source records attributed to Vlastimil Hruska.

6 recordsLinked to original sources

Kohlrausch regulating function and other conservation laws in electrophoresis.

The Kohlrausch regulating function (KRF) is a conservation law (conservation function), which is held in electrophoresis and which enables calculation of the so-called adjusted concentrations of constituents. The KRF is not the only conservation function and, depending on the complexity of the electrophoretic system, other conservation laws may be obeyed having a broader range of applicability. The conservation laws are tightly related to system eigenmobilities and system zones (system peaks). In principle, no system eigenmobility is exactly zero, but in most practical cases at least one system's eigenmobility is close to zero. The existence of the close-to-zero eigenmobility inherently points to the existence of a conservation function and a system zone which is stationary. The stationary system zone is called injection zone, stagnant zone, water peak, or solvent dip. Electrophoretic (electromigration) systems can be divided into two types: (i) conservation systems, in which the absolute value of at least one system eigenmobility is close to zero and where at least one conservation law is obeyed and (ii) nonconservation systems, where no system eigenmobility is close to zero and no conservation law is obeyed. The paper reviews work dealing with conservation functions in electromigration, derives some "historical" conservation functions in a new way, derives several conservation functions for systems of multivalent electrolytes, and discusses electrophoretic systems that have nonconservation behavior. In some typical instances, the conservation functions are simulated by means of a dynamic simulation tool and depicted graphically.

Chemical Phenomena↗

Oscillating electrolytes.

Chemical oscillations are driven by the gradient of the chemical potential so that they can appear in systems where the substances are not in chemical equilibrium. We show that under the influence of the electric field, concentrations of electrically charged substances in solutions can oscillate even if the system is in chemical equilibrium. The driving force here is not the gradient of the chemical potential but rather the gradient of the electric potential. Utilizing CE we found periodic structures invoked by the application of a constant driving voltage in BGEs possessing complex eigenmobilities. By analogy with the behavior of dynamic systems, complex eigenmobilities implicate that the system will be unstable. Instead of forming system zones (system peaks) in the separation channel (capillary) the originally uniform concentration of electrolyte constituents becomes periodically disturbed when the electric current passes through it.

Electrolytes↗

Simul 5 - free dynamic simulator of electrophoresis.

We introduce the mathematical model of electromigration of electrolytes in free solution together with free software Simul, version 5, designed for simulation of electrophoresis. The mathematical model is based on principles of mass conservation, acid-base equilibria, and electroneutrality. It accounts for any number of multivalent electrolytes or ampholytes and yields a complete picture about dynamics of electromigration and diffusion in the separation channel. Additionally, the model accounts for the influence of ionic strength on ionic mobilities and electrolyte activities. The typical use of Simul is: inspection of system peaks (zones), stacking and preconcentrating analytes, resonance phenomena, and optimization of separation conditions, in either CZE, ITP, or IEF.

Computer Simulation↗

Eigenmobilities in background electrolytes for CZE. V. Intensity (amplitudes) of system peaks.

We present a mathematical model of CZE based on the concept of eigenmobilities - the eigenvalues of matrix M tied to the linearized governing equations of electromigration, and the spectral decomposition of matrix M into matrices of amplitudes P(j). Any peak in an electropherogram, regardless of whether it is an analyte peak or a system peak (system zone), is matched with its matrix P(j). This enables calculation of the peak parameters, such as the transfer ratio and the molar conductivity detection response (which give the indirect detection signal and the conductivity detection signal, respectively), when the initial disturbance caused by the injection of the sample is known. We also introduce new quantities, such as the generalized transfer ratio and the conductivity response of system zones, and show how the amplitude (intensity, area) of the analyte peaks and the system peaks can be calculated. We offer a free software, PeakMaster (http://www.natur.cuni.cz/gas), which yields this information in a user-friendly way.

Acetic Acid↗

Eigenmobilities in background electrolytes for capillary zone electrophoresis: III. Linear theory of electromigration.

A mathematical model of capillary zone electrophoresis (CZE) based on the conception of eigenmobilities, which are the eigenvalues of a matrix M tied to the linearized governing equations is presented. The model considers CZE systems, where constituents, either analytes or components of the background electrolyte (BGE), are weak electrolytes--acids, bases, or ampholytes. There is no restriction on the number of components nor on the valence of the constituents nor on pH of the BGE. An electrophoretic system with N constituents has N eigenmobilities. In most BGEs one or two eigenmobilities are very close to zero so their corresponding eigenzones move very slowly. However, there are BGEs where no eigenmobility is close to zero. The mathematical model further provides: the transfer ratio, the molar conductivity detection response, and the relative velocity slope. This allows the assessment of the indirect detection, conductivity detection and peak broadening (distortion) due to electromigration dispersion. Also, we present a spectral decomposition of the matrix M to matrices allowing the assessment of the amplitudes of system eigenpeaks (system peaks). Our model predicted the existence of BGEs having no stationary injection zone (or water zone, gap, peak, dip). A common practice of using the injection zone as a marker of the electroosmotic flow must fail in such electrolytes.

Buffers↗

Eigenmobilities in background electrolytes for capillary zone electrophoresis: IV. Computer program PeakMaster.

We are introducing a computer implementation of the mathematical model of zone electrophoresis (CZE) described in Stedry, M., Jaros, M., Hruska, V., Gas, B., Electrophoresis 2004, 25, 3071-3079 program PeakMaster. The computer model calculates eigenmobilities, which are the eigenvalues of the matrix tied to the linearized continuity equations, and which are responsible for the presence of system eigenzones (system zones, system peaks). The model also calculates other parameters of the background electrolyte (BGE)-pH, conductivity, buffer capacity, ionic strength, etc., and parameters of the separated analytes--effective mobility, transfer ratio, molar conductivity detection response, and relative velocity slope. This allows the assessment of the indirect detection, conductivity detection and peak broadening (peak distortion) due to electromigration dispersion. The computer model requires the input of the BGE composition, the list of analytes to be separated, and the system instrumental configuration. The output parameters of the model are directly comparable with experiments; the model also simulates electropherograms in a user-friendly way. We demonstrate a successful application of PeakMaster for inspection of BGEs having no stationary injection zone.

Computer Simulation↗