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Determination of adsorption isotherms in supercritical fluid chromatography
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences.
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences.
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences.ORCID iD: 0000-0003-1819-1709
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences.
2013 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1312, 124-133 p.Article in journal (Refereed) Published
Abstract [en]

Abstract In this study we will demonstrate the potential of modern integrated commercial analytical SFC-systems for rapid and reliable acquisition of thermodynamic data. This will be done by transferring the following adsorption isotherm determination methods from liquid chromatography (LC) to supercritical fluid chromatography (SFC): Elution by Characteristic Points (ECP), the Retention Time Method (RTM), the Inverse Method (IM) and the Perturbation Peak (PP) method. In order to transfer these methods to SFC in a reliable, reproducible way we will demonstrate that careful system verification using external sensors of mass flow, temperature and pressure are needed first. The adsorption isotherm data generated by the different methods were analyzed and compared and the adsorption isotherms ability to predict new experimental elution profiles was verified by comparing experiments with simulations. It was found that adsorption isotherm data determined based on elution profiles, i.e., ECP, IM and RTM, were able to accurately predict overloaded experimental elution profiles while the more tedious and time-consuming PP method, based on small injections on concentration plateaus, failed in doing so.

Place, publisher, year, edition, pages
2013. Vol. 1312, 124-133 p.
Keyword [en]
Adsorption isotherms, Elution by Characteristic Points, Inverse method, Perturbation Peak method, Retention Time Method, Supercritical fluid chromatography
National Category
Physical Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kau:diva-34380DOI: 10.1016/j.chroma.2013.09.007ISI: 000325123200016PubMedID: 24041510OAI: oai:DiVA.org:kau-34380DiVA: diva2:755855
Available from: 2014-10-15 Created: 2014-10-15 Last updated: 2015-09-25Bibliographically approved
In thesis
1. Fundamental Investigations of Supercritical Fluid Chromatography
Open this publication in new window or tab >>Fundamental Investigations of Supercritical Fluid Chromatography
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis aims at a deeper understanding of Supercritical Fluid

Chromatography (SFC). Although preparative SFC has started to replace Liquid Chromatography (LC) in the pharmaceutical industry - because of its advantages in speed and its less environmental impact - fundamental understanding is still lacking. Therefore there is no rigid framework to characterize adsorption or to understand the impact of changes in operational conditions.

 

In Paper I we demonstrated, after careful system verification, that most methods applied to determine adsorption isotherms in LC could not be applied directly in SFC. This was mainly due to operational differences and to the fact that the fluid is compressible which means that everything considered constant in LC varies in SFC.

 

In Paper II we showed that the most accurate methods for adsorption isotherm determination in LC, the so called plateau methods, do not work properly for SFC. Instead, methods based on overloaded profiles should be preferred.

 

In Paper III a Design of Experiments approach was successfully used to quantitatively describe the retention behavior of several solutes and the productivity of a two component separation system. This approach can be used to optimize SFC separations or to provide information about the separation system.

 

In Paper IV severe peak distortion effects, suspected to arise from injection solvent and mobile phase fluid mismatches, were carefully investigated using experiments and simulations. By this approach it was possible to examine the underlying reasons for the distortions, which is vital for method development.

 

Finally, in Paper V, the acquired knowledge from Paper I-IV was used to perform reliable scale-up in an industrial setting for the first time. This was done by carefully matching the conditions inside the analytical and preparative column with each other. The results could therefore provide the industry with key knowledge for further implementation of SFC.

Abstract [en]

This thesis aims at a deeper understanding of Supercritical Fluid

Chromatography (SFC). Although preparative SFC has started to replace Liquid Chromatography (LC) in the pharmaceutical industry - because of its advantages in speed and its less environmental impact - fundamental understanding is still lacking. Therefore there is no rigid framework to characterize adsorption or to understand the impact of changes in operational conditions.

 

In Paper I-II it was demonstrated why most methods applied to determine adsorption isotherms in LC could not be applied directly for SFC. Methods based on extracting data from overloaded profiles should be preferred.

 

In Paper III a Design of Experiments approach was successfully used to quantitatively describe the behavior of several solutes in a

separation system. This approach can be used to optimize SFC separations or to provide information about the separation system.

 

In Paper IV severe peak distortion effects often observed in SFC were carefully investigated and explained using experiments and simulations.

 

Finally, in Paper V, the prerequisites for performing reliable and predictable scale-up of SFC were investigated by small and large scale experiments.

Place, publisher, year, edition, pages
Karlstad: Karlstads universitet, 2015. 63 p.
Series
Karlstad University Studies, ISSN 1403-8099 ; 2015:45
Keyword
Supercritical Fluid Chromatography, SFC, Modeling, Adsorption Isotherms, Scale-up, Peak Distortion, Injection, Design of Experiments, Perturbation Peak Method, Elution by Characteristic Points Method, Method transfer
National Category
Analytical Chemistry Chemical Engineering
Research subject
Chemistry
Identifiers
urn:nbn:se:kau:diva-37913 (URN)978-91-7063-663-9 (ISBN)
Public defence
2015-10-16, Nyquistsalen 9C 203, Karlstads universitet, Karlstad, 10:15 (English)
Opponent
Supervisors
Note

Paper 4 ("Evaluation of scale-up from analytical to preparative...") ingick som manuskript med samma titel i avhandlingen. Nu publicerad. 

Available from: 2015-09-25 Created: 2015-09-11 Last updated: 2016-03-08Bibliographically approved

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Enmark, MartinForssén, PatrikSamuelsson, JörgenFornstedt, Torgny
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