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Supercritical Fluid Chromatography of Organic Bases Using a Modified Water Stationary Phase

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Abstract

A supercritical fluid chromatography-flame ionization detection (SFC-FID) system employing a modified water stationary phase has been investigated for use in the analysis of organic bases. The method uses a stainless steel capillary column coated with water containing 0.5–1 M NH4OH, which is also used to hydrate the system. In this way, the pH of the water stationary phase can be effectively altered to help control the ionization of organic base analytes and greatly improve their peak shape and elution properties. This is in contrast to the poor results observed on a pure water stationary phase for basic analytes, which occurs due to their charged state in the otherwise naturally acidic CO2/water phase interface. Overall, the NH4OH modified system provided reliable FID response and showed good performance over a wide range of column temperatures and CO2 pressures, respectively, tested up to about 150 °C and 200 atm. Under isothermal conditions, some system instability usually began to onset at higher pressures, and the level needed for this also increased with temperature. The results show that this approach can be useful for the successful elution of bases over a wide range of pKa values (tested up to 10.4). Further, retention on the phase shows partial correlation to analyte pKa, but little relationship to boiling point. The method was successfully applied to the analysis of organic bases in several complex matrices, including the separation and detection of pharmaceuticals and their degradants. The results indicate that this SFC-FID method could be potentially beneficial to further explore for the analysis of organic bases in a variety of areas.

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Acknowledgements

The authors are grateful to the Natural Sciences and Engineering Research Council of Canada (NSERC) for a Discovery Grant in support of this project.

Funding

This study was funded by an NSERC Discovery Grant.

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Authors and Affiliations

  1. Department of Chemistry, University of Calgary, 2500 University Drive, NW, Calgary, AB, T2N 1N4, Canada

    Emmanuel A. Nai & Kevin B. Thurbide

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  1. Emmanuel A. Nai
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  2. Kevin B. Thurbide
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Correspondence to Kevin B. Thurbide.

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Nai, E.A., Thurbide, K.B. Supercritical Fluid Chromatography of Organic Bases Using a Modified Water Stationary Phase. Chromatographia 85, 1087–1096 (2022). https://doi.org/10.1007/s10337-022-04208-1

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  • DOI: https://doi.org/10.1007/s10337-022-04208-1

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