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Petr Bocek

Publications and source records attributed to Petr Bocek.

22 records · Page 2Linked to original sources

Multivalent weak electrolytes - risky background electrolytes for capillary zone electrophoresis.

Multivalent weak acids and bases are useful components of buffers in electrophoresis. The use of such buffers as background electrolytes (BGEs) in capillary zone electrophoresis (CZE) is, however, risky due to the existence of unsafe regions in the analytical window of the separation. This contribution discusses the problems and shows that multivalent weak species in BGEs bring about the same effects as mixtures of two independent co-ions, i.e., the presence of two centers of symmetry in the electropherograms and the existence of a migrating system zone with a mobility in between these two centers of symmetry. The system zone deteriorates the analytical separation and detection of the analytes in its neighborhood. Illustrative experimental examples for both cationic and anionic CZE are shown and related discussion is given. Finally, some basic rules are formulated to avoid the preparation of risky BGEs.

Acids↗

Multiple effect of surfactants used as additives in background electrolytes in capillary zone electrophoresis: cetyltrimethylammonium bromide as example of model surfactant.

Surfactants are frequently used in the preparation of background electrolytes (BGEs) in capillary zone elcetrophoresis (CZE) in order to affect and to optimize both the electroosmotic flow (EOF) and the separation process. Their effects are, however, always multiple, the resulting situation may be very complex and the separation process may even be destroyed. We use the surfactant cetyltrimethylammonium bromide (CTAB) as a model example and bring experimental results and related discussion which elucidate the multiple effect of surfactants in an integrated way. It is shown that even at concentration levels lower than 10(-4) M CTAB strongly reduces the cathodic EOF in bare fused-silica capillaries and converts it into anodic EOF. The magnitude and polarity of the EOF depends not only on the concentration of CTAB but also on the composition of BGEs used. The interactions of CTA cations with the bare capillary wall reduce sorption of cationic analytes and enables their analysis. CTA cations at levels below their critical micelles concentration (CMC) already interact with anionic analytes and reduce their mobilities. This association is strong with highly charged anions and by this, the reversal of the EOF, applying BGEs with highly charged anions is less effective. These interactions are competitive and also depend on the composition of the BGE used. At levels above its CMC, CTAB forms micelles and enables the application of the micellar electrokinetic capillary chromatography (MEKC) mode and the analysis of, e.g., neutral components. Simultaneously, it is shown that the presence of CTAB may increase the number of potentially formed system zones.

Cetrimonium↗

Fast choice of separation conditions for analyses by capillary zone electrophoresis using an information system Xemic.

An information system Xemic applicable in analytical chemistry is described and its use in capillary electrophoresis for searching suitable separation conditions is demonstrated. This system is capable to provide suitable separation conditions even for analytes for which no electrophoretic experiments have been published so far. The system works with a database of components of anionic character the analyses of which have been performed, published in reviewed scientific journals, and included into a database created by an expert. Moreover, the system learned to search also in abstracts or complete scientific articles to find articles dealing with the determination of a substance in a given sample matrix. When no experiments have been published so far for a defined substance in a specific matrix, Xemic shows the separation conditions for determination of the substance regardless of the matrix. When no response can be found for the analyte of interest at all, the system Xemic works like an expert in the field and searches chemically similar substances and offers a series of substances the physicochemical properties of which are close to the followed analyte with respect to the behavior in the electric field, and shows working conditions for their analysis. Thus, the analyst puts only the order in the form of a given analyte in a given matrix and obtains a recommendation of a separation system that should enable to perform a successful separation. The system is not rigid and enables the operator to change the importance of individual attributes used in similarity search so as to obtain a broader or narrower group of similar components. With a certain probability the analyte of interest can be successfully analyzed under separation conditions that suited for the analysis of the most similar substances in the given matrix.

Computers↗

Recent progress in capillary isotachophoresis.

This article is a continuation of previous reviews and summarizes the progress of analytical capillary isotachophoresis since 2000. Papers reviewed include methodological and instrumental aspects as well as analytical applications. Included are also papers using isotachophoresis and/or isotachophoretic principles as part of multidimensional separation schemes.

Electrophoresis, Capillary↗