Simulation of the effects of complex‐ formation equilibria in electrophoresis: II. Experimental verification

Svobodová, Jana; Beneš, Martin; Hruška, Vlastimil; Ušelová, Kateřina; Gaš, Bohuslav

doi:10.1002/elps.201100503

Cited by 43 publications

(55 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The new versions of GENTRANS and SIMUL5complex allow the study of the impact of chemical equilibria other than protolysis on the dynamics of electrophoretic separations. They comprise algorithms to account for the interaction with an electrolyte additive.…”

Section: Methodsmentioning

confidence: 99%

“…Dubrovčáková et al presented a mathematical model and numerical solution for the addition of a neutral complexation agent to moving‐boundary systems of strong electrolytes, including the migration of an ITP zone. Recently, GENTRANS and SIMUL5, the latter program referred to as SIMUL5complex , were extended with algorithms that describe 1:1 chemical equilibria between solutes and a buffer additive. These models were found to properly describe the dynamics of chiral separations via use of complexation constants and specific mobilities of formed analyte‐selector complexes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dynamic high‐resolution computer simulation of isotachophoretic enantiomer separation and zone stability

2014

View full text Add to dashboard Cite

The development of electrophoretic computer models and their use for simulation of electrophoretic processes has increased significantly during the last few years. Recently, GENTRANS and SIMUL5 were extended with algorithms that describe chemical equilibria between solutes and a buffer additive in a fast 1:1 interaction process, an approach that enables simulation of the electrophoretic separation of enantiomers. For acidic cationic systems with sodium and H3 0(+) as leading and terminating components, respectively, acetic acid as counter component, charged weak bases as samples, and a neutral CD as chiral selector, the new codes were used to investigate the dynamics of isotachophoretic adjustment of enantiomers, enantiomer separation, boundaries between enantiomers and between an enantiomer and a buffer constituent of like charge, and zone stability. The impact of leader pH, selector concentration, free mobility of the weak base, mobilities of the formed complexes and complexation constants could thereby be elucidated. For selected examples with methadone enantiomers as analytes and (2-hydroxypropyl)-β-CD as selector, simulated zone patterns were found to compare well with those monitored experimentally in capillary setups with two conductivity detectors or an absorbance and a conductivity detector. Simulation represents an elegant way to provide insight into the formation of isotachophoretic boundaries and zone stability in presence of complexation equilibria in a hitherto inaccessible way.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dynamic high‐resolution computer simulation of isotachophoretic enantiomer separation and zone stability

2014

View full text Add to dashboard Cite

show abstract

“…The electrophoretic processes occurring in this complex system are herein described utilizing computer simulation with the software SIMUL5complex. SIMUL5complex is a 1D dynamic electrophoresis simulator that includes algorithms to describe 1:1 equilibria between solutes and a (neutral, monovalent or polyvalent) buffer additive and can be downloaded as freeware from http://echmet.natur.cuni.cz/download. Complexation constants, K , between the interacting species and the chiral selector and mobilities of the formed complexes, u c , are required as input.…”

Section: Input Parameters For Simulationsmentioning

confidence: 99%

Computer simulation of the enantioselective separation of weak bases in an online capillary electrophoresis based microanalysis configuration comprising sulfated cyclodextrin as selector

Mikkonen

Thormann

2018

Electrophoresis

View full text Add to dashboard Cite

Computer simulation was utilized to characterize the electrophoretic processes occurring after reactant mixing in an online assay format used for monitoring the enantioselective N-demethylation of ketamine to norketamine in the presence of highly sulfated γ-cyclodextrin (HS-γ-CD). The incubated reaction mixture (at pH 7.4 and without chiral selector) is bracketed by a low pH BGE containing 2% HS-γ-CD as chiral selector, thereby forming a discontinuous buffer system. Upon power application, simulation provides insight into the formation of moving boundaries and new zones together with the prediction of the behavior of ketamine and norketamine enantiomers. The analytes first migrate cationically in a zone electrophoretic manner until they come in contact with HS-γ-CD upon which enantioseparation is initiated. Complexation has a focusing effect and the electrophoretic transport becomes reversed, that is, toward the anode. Simulation revealed that the initial conditions for the chiral separation, including buffer components concentrations, pH, and ionic strength, are different than those in the BGE. As a consequence thereof, the experimentally determined complexation parameters for the BGE were unable to correctly describe the migration behavior of the analytes in this column section. An increase in the input binding constants by a factor of two to four, as a result of the decreased ionic strength, resulted in simulation data that agreed with experimental findings.

show abstract

“…In 2012, a complete theoretical model of electromigration for complex forming systems was presented by our research group . This model was implemented into our simulation program Simul 5 Complex and verified experimentally . Very good agreement of experimental and simulated data was achieved.…”

Section: Introductionmentioning

confidence: 99%

Applicability and limitations of affinity capillary electrophoresis and vacancy affinity capillary electrophoresis methods for determination of complexation constants

et al. 2013

Self Cite

View full text Add to dashboard Cite

ACE and vacancy affinity capillary electrophoresis (VACE) are the commonly used methods for determination of complexation constants by CE. The applicability and limitations of these methods were tested experimentally and by means of simulations using our simulation software Simul 5 Complex. It was shown that while the ACE method provides reliable and precise values of complexation parameters, those determined by VACE can be incorrect especially in the case of strong complexation. The effective mobilities of the system peaks in the VACE method, and consequently, the resulting complexation parameters were found to be a function of concentration of the analyte present in the BGE. Development of system peaks in VACE is discussed in the frame of the linear theory of electromigration. Dependence of mobility of system peaks on the composition of the BGE cannot be characterized by a simple analytical expression as in the case of ACE method. Thus, the VACE method fails and the resulting complexation constants might seriously differ from the reality.

show abstract

Simulation of the effects of complex‐ formation equilibria in electrophoresis: II. Experimental verification

Cited by 43 publications

References 47 publications

Dynamic high‐resolution computer simulation of isotachophoretic enantiomer separation and zone stability

Dynamic high‐resolution computer simulation of isotachophoretic enantiomer separation and zone stability

Computer simulation of the enantioselective separation of weak bases in an online capillary electrophoresis based microanalysis configuration comprising sulfated cyclodextrin as selector

Applicability and limitations of affinity capillary electrophoresis and vacancy affinity capillary electrophoresis methods for determination of complexation constants

Contact Info

Product

Resources

About