Molecular theory of size exclusion chromatography for wide pore size distributions

•A novel theory of SEC for wide pore size distribution is introduced.•Wide pore size distribution improves the efficiency when macromolecules are separated.•The pore size distribution of HPLC stationary phases can conveniently be calculated. Chromatographic processes can conveniently be modeled at a...

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Bibliographic Details
Published in:Journal of Chromatography A 2014-02, Vol.1331, p.52-60
Main Authors: Sepsey, Annamária, Bacskay, Ivett, Felinger, Attila
Format: Article
Language:English
Subjects:
Analytical chemistry
Chemistry
Chromatographic methods and physical methods associated with chromatography
Chromatography
Egress
Estimates
Exact sciences and technology
Heterogeneity
Molecular theory
Other chromatographic methods
Pore size
Pore size distribution
Porosity
Size exclusion chromatography
Stochastic theory
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Summary:•A novel theory of SEC for wide pore size distribution is introduced.•Wide pore size distribution improves the efficiency when macromolecules are separated.•The pore size distribution of HPLC stationary phases can conveniently be calculated. Chromatographic processes can conveniently be modeled at a microscopic level using the molecular theory of chromatography. This molecular or microscopic theory is completely general; therefore it can be used for any chromatographic process such as adsorption, partition, ion-exchange or size exclusion chromatography. The molecular theory of chromatography allows taking into account the kinetics of the pore ingress and egress processes, the heterogeneity of the pore sizes and polymer polydispersion. In this work, we assume that the pore size in the stationary phase of chromatographic columns is governed by a wide lognormal distribution. This property is integrated into the molecular model of size exclusion chromatography and the moments of the elution profiles were calculated for several kinds of pore structure. Our results demonstrate that wide pore size distributions have strong influence on the retention properties (retention time, peak width, and peak shape) of macromolecules. The novel model allows us to estimate the real pore size distribution of commonly used HPLC stationary phases, and the effect of this distribution on the size exclusion process.
ISSN:0021-9673
DOI:10.1016/j.chroma.2014.01.017