National Repository of Grey Literature 105 records found  previous11 - 20nextend  jump to record: Search took 0.01 seconds. 
Software Tools for Optimization of Background Electrolytes in Electrophoresis
Hruška, Vlastimil ; Gaš, Bohuslav (advisor) ; Gebauer, Petr (referee) ; Kašička, Václav (referee)
7. Results The aim of my PhD. thesis was development of software tools for optimization of background electÍolytes in electrophoresis, study of system peak and general theory of electromigration. During my study I cooperated on the programming of the program PeakMaster 5 and I implemented theory of amplitudes to it (PeakMaster 5.2). The main subject of my work was development of the program Simul 5. During my study I added several new features, which significantly improved is capabilities and fields of applications. Both prcgrams are often used at many universities all over the world. Especially, program PeakMaster is very popular among wide range of users thank to its fast calculation of pH with very good ionic strength correction. Funher, I cooperated on finding of some reď systems, whose prediction was based on linearization of electromigration problem and properties of system peal6 such as discovery of oscillating electrolytes, systems without stationary system zones (without regulation functions) or urilization of system peaks in micellar electrophoresis for determination of CMC of micelles. . .!r ! Li-a.. --,;ared in the following qhaBlers.
Influence of the interacting constituent of the background electrolyte on electrophoretic separation
Müllerová, Ludmila ; Dubský, Pavel (advisor) ; Kašička, Václav (referee) ; Petr, Jan (referee)
Capillary electrophoresis is a widely used separation method of analytical chemistry. Addition of a selector into the background electrolyte extends its applicability to separation of enantiomers or of compounds of similar physicochemical properties. In analytical practice, mixtures of selectors are also commonly used - either prepared intentionally to achieve better separation or because commercially available selectors may be mixtures of compounds differing in the degree of substitution and substituent positions. Mathematical description of these systems, which are highly relevant in analytical practice, can simplify search for optimal separation conditions. Also, it provides a useful insight into the separation mechanism. In this work, a model of electromigration of an analyte interacting with a mixture of two selectors is proposed and experimentally verified. This model results from a more general description of systems with an arbitrary number of selectors. The model shows that a selector mixture can be treated as a single selector if the ratio of the respective selector concentrations is kept constant. When the mixture is prepared intentionally, this description predicts, how separation potential of the mixture changes with its composition. Thus it allows the optimal composition and total...
Chiral separation of diquats and determination of stability constants of their complexes with cyclodextrins by capillary electrophoresis
Bílek, Jan ; Kašička, Václav (advisor) ; Jelínek, Ivan (referee)
Capillary zone electrophoresis was used for chiral separation of eleven diquat derivatives. These N-heteroaromatic dications containing structural motif of 2,2'-bipyridine have recently been studied for their interesting electrochemical properties as well as for the axial chirality of their molecules. The combination of these properties could potencially lead to interesting applications in the future. For enantioseparation of diquats (DQ) commercially available randomly sulfated α-, β-, and γ-cyclodextrins with high degree of substitution were used. A succesfull chiral separation was achieved using all of the three sulfated cyclodextrins as chiral selectors (CS). Baseline enantioseparation was achieved for 82 %, 91 % respectively 100 % of the analyzed DQ in the presence of HS-α-CD, HS-β-CD, HS-γ-CD respectively. The highest separation efficiency and resolution were obtained in the backround electrolyte containing 22 mmol/L NaOH, 35 mmol/L H3PO4 (pH2,5) and 6 mmol/L HS-β-CD. Using three available nonracemic DQ an identification of the particular M- and P-enantiomers was done for the three corresponding DQ structures. Apparent stabillity constants of complexes of the DQ derivatives with above mentioned cyclodextrins as CS were determined by means of capillary affinity electrophoresis. The stability...
The Determination and Comparison of the Electromigration Properties of Markers for Isoelectric Focusing
Lorinčíková, Kateřina ; Gaš, Bohuslav (advisor) ; Kašička, Václav (referee)
The dependencies of electrophoretic mobility on pH were measured for a set of 14 markers used for isoelectric focusing that were developed by the group of Šlais and that are based on substitutions on the nitrophenol core, and for a kit consisting of 5 pI markers developed by Shimura, which have an oligopeptide structure. The dissociation constants and limiting electrophoretic mobilities of these compounds were obtained from the dependencies with the use of the program AnglerFish. The isoelectric point values of the compounds were consequently calculated using the obtained data. A comparison of the obtained pI values with the values that have been declared in literature, albeit gained by different analytical methods, has been made. Key Words capillary zone electrophoresis, isoelectric focusing, pI markers, isoelectric point, thermodynamic dissociation constant, limiting ionic mobility
Mathematical modelling of linear and nonlinear phenomena in capillary electrophoresis
Dvořák, Martin ; Dubský, Pavel (advisor) ; Kašička, Václav (referee) ; Gebauer, Petr (referee)
Capillary electrophoresis is one of the prominent analytical separation methods. Currently, many computer programs exist which are able to predict the result of an electrophoretic experiment. Firstly, there are programs based on numerical solving of corresponding continuity equations and equations of chemical equilibria. Secondly, there are programs based on approximative models of capillary electrophoresis. Programs belonging to the first group are applicable to a wide range of modes of capillary electrophoresis and provide a precise solution. Their disadvantage is though a considerable time demand. On the other hand, the approximative models give the results almost immediately and, in addition, provide some theoretical relationships which are useful for optimization of the separation process. This dissertation thesis is focused on improvement and extension of validity of existing approximative models of capillary electrophoresis. As a part of this thesis, a model capable of a full-blown description of capillary electrokinetic chromatography is introduced. This model is implemented into program PeakMaster 6. The attention is also paid to a nonlinear model of electromigration without diffusion. This model enables a very good description of electromigration dispersion including effects related to...
Determination of binding constants of human insulin complexes with serotonin, dopamine, arginine, and phenol by pressure assisted partial filling affinity capillary electrophoresis
Šolínová, Veronika ; Žáková, Lenka ; Jiráček, Jiří ; Kašička, Václav
A new method, pressure assisted partial filling affinity capillary electrophoresis (PF-ACE), has been developed to study noncovalent interactions of the hexamer of human insulin (HI) with cationic ligands, such as phenolic neurotransmitters serotonin and dopamine, and amino acid arginine, or with anionic ligand phenol, in alkaline aqueous solutions. The apparent binding constants, Kb, of the HI-ligand complexes were determined from the dependence of the effective migration time changes of the above ligands on the variable zone lengths of HI dissolved in the background electrolyte and hydrodynamically introduced into the bare fused silica capillary close to the UV detector. The HI interactions with the above ligands were found to be moderately strong, with Kb values in the range 385-1314 L/mol.
Enantioseparation and estimation of racemization barriers of selected helquats and their derivatives by capillary electrophoresis using sulfated cyclodextrins as chiral selectors
Sázelová, Petra ; Koval, Dušan ; Severa, Lukáš ; Reyes Gutierrez, Paul Eduardo ; Jirásek, Michael ; Teplý, Filip ; Kašička, Václav
Anionic highly sulfated β- and γ-cyclodextrins (S-CDs) and single-isomer heptakis-(2,3-diacetyl-6-sulfato)-β-CD (14Ac-7S-β-CD) were used for chiral separation of [5], [6] and [7]-ring helquats and helquat styryl dyes by capillary electrophoresis (CE) in the background electrolyte composed of 22 mM NaOH/35 mM H3PO4, pH 2.4. The CE method was applied for monitoring of racemization of eight helquats and helical dyes. Rate constant k of conversion, half-life T1/2 of racemization, and activation Gibbs free energy ΔGǂ of interconversion of one enantiomer into the other were calculated from the dependence of natural logarithm of enantiomeric excess (ee) on time using linear regression analysis.
Separation of rotamers of 5-nitrosopyrimidines by capillary electrophoresis
Štěpánová, Sille ; Procházková, Eliška ; Čechová, Lucie ; Žurek, Jiří ; Janeba, Zlatko ; Dračínský, Martin ; Kašička, Václav
A new capillary electrophoresis (CE) method was developed for the separation of a new type of stereoisomers - rotamers of polysubstituted 5-nitrosopyrimidine derivatives. Partial separation of some rotamers was obtained in sodium borate, pH 9.3, or in Tris-phosphate, pH 2.2, background electrolytes (BGEs) free of cyclodextrins (CDs). However, the best, baseline separations of the rotamers of 5-nitrosopyrimidines were achieved in sodium borate BGE, pH 9.3, containing 20 mg/mL beta-CD as stereoselector, or in Tris-phosphate BGE, pH 2.2, with carboxymethyl-beta-CD as stereoselector.
Monitoring of enzymatic enantioselective acetylation of gem-difluorinated alcohols by capillary electrophoresis
Šolínová, Veronika ; Pomeisl, Karel ; Lamatová, Nikola ; Pohl, Radek ; Brabcová, Jana ; Krečmerová, Marcela ; Kašička, Václav
A new fast and highly efficient capillary electrophoretic (CE) method has been developed for chiral analysis of non-charged gem-difluorinated alcohol (3-(benzyloxy)-1,1-difluoro-propan-2-ol) using sulfobutylether-β-CD as chiral selector. The method was applied for monitoring of enzymatic (lipase mediated) enantioselective acetylation of the above alcohol and for determination of enantiomeric purity of both substrates and products of the enzymatic reaction.
Estimation of binding constants of associates of Ru(II) and Fe(II) polypyridyl complexes with single-isomer sulfated cyclodextrins by capillary electrophoresis
Sázelová, Petra ; Koval, Dušan ; Severa, Lukáš ; Teplý, Filip ; Kašička, Václav
Capillary electrophoresis (CE) was applied for enantioseparations of [Ru(bpy)3]2+, [Ru(phen) 3]2+ and [Fe(phen) 3]2+ complexes and for the estimation of binding constants of their associates with selected single-isomer sulfated cyclodextrins (SCDs). The apparent binding constants of the complexes of [Ru(bpy)3]2+, [Ru(phen)3]2+, and [Fe(phen)3]2+ enantiomers with the above SCDs were determined from the dependence of their effective electrophoretic mobilities on the concentration of the SCDs in the background electrolyte. Calculated apparent binding constants were found to be smaller than those obtained for randomly sulfated SCDs.

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