View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Digital Repository @ Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 2007 Enantiomeric separations on cyclodextrin-based and synthetic polymeric chiral stationary phases by high performance liquid chromatography and supercritical fluid chromatography Xinxin Han Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Analytical Chemistry Commons Recommended Citation Han, Xinxin, "Enantiomeric separations on cyclodextrin-based and synthetic polymeric chiral stationary phases by high performance liquid chromatography and supercritical fluid chromatography" (2007). Retrospective Theses and Dissertations. 15599. https://lib.dr.iastate.edu/rtd/15599 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Enantiomeric separations on cyclodextrin-based and synthetic polymeric chiral stationary phases by high performance liquid chromatography and supercritical fluid chromatography by Xinxin Han A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Analytical Chemistry Program of Study Committee: Daniel W. Armstrong, Co-major Professor Robert S. Houk, Co-major Professor Jacob W. Petrich Klaus Schmidt-Rohr George A. Kraus Iowa State University Ames, Iowa 2007 Copyright © Xinxin Han, 2007. All rights reserved. UMI Number: 3289401 UMI Microform 3289401 Copyright 2008 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, MI 48106-1346 ii Table of Contents Abstract................................................................................................................................... vii Chapter 1. General introduction.................................................................................................1 1.1. Introduction.....................................................................................................................1 1.2. Macrocyclic CSPs...........................................................................................................1 1.2.1. Chiral crown ether based CSPs................................................................................2 1.2.2. Cyclodextrin based CSPs.........................................................................................2 1.2.3. Macrocyclic glycopeptide based CSPs ....................................................................3 1.3. π-π association CSPs.......................................................................................................4 1.4. Polymeric CSPs ..............................................................................................................4 1.4.1. CSPs based on natural polymers..............................................................................4 1.4.2. CSPs based on synthetic polymers ..........................................................................6 1.5. Applications of CSPs on packed column SFC................................................................8 1.6. Summary.........................................................................................................................8 1.7 Dissertation Organization ................................................................................................9 References..............................................................................................................................9 Chapter 2. Separation of chiral furan derivatives by liquid chromatography using cyclodextrin-based chiral stationary phases ............................................................................24 Abstract................................................................................................................................24 2.1. Introduction...................................................................................................................24 2.2. Experimental.................................................................................................................26 2.2.1. Materials ................................................................................................................26 2.2.2. Preparation of chiral furan derivatives...................................................................26 2.2.3. Equipment ..............................................................................................................26 2.2.4. Column Evaluation ................................................................................................26 2.2.5. Calculations............................................................................................................27 2.3. Results and discussion ..................................................................................................27 2.3.1. Performance of the CSPs .......................................................................................27 2.3.2. Effect of mobile phase composition.......................................................................28 2.4. Conclusions...................................................................................................................31 iii Acknowledgements..............................................................................................................32 References............................................................................................................................32 Chapter 3. Separation of enantiomers of isochromene derivatives by HPLC using cyclodextrin-based stationary phases.......................................................................................46 Abstract................................................................................................................................46 3.1. Introduction...................................................................................................................46 3.2. Experimental.................................................................................................................47 3.2.1. Materials ................................................................................................................47 3.2.2. Equipment ..............................................................................................................48 3.2.3. Column Evaluation ................................................................................................48 3.2.4.Calculations.............................................................................................................48 3.3. Results and Discussion .................................................................................................49 3.3.1. Performance of the 8 CSPs in the 3 Separation Modes .........................................49 3.3.2. Effect of Mobile Phase Composition in the Reverse Phase Mode ........................50 3.3.3. Effects of Substituents on the Isochromene Ring..................................................50 3.4. Conclusions...................................................................................................................52 Acknowledgements..............................................................................................................52 References............................................................................................................................52 Chapter 4. Enantiomeric separation of fused polycycles by HPLC with cyclodextrin and macrocyclic glycopeptide chiral stationary phases..................................................................63 Abstract................................................................................................................................63 4.1. Introduction...................................................................................................................63 4.2. Experimental.................................................................................................................64 4.2.1. Materials ................................................................................................................64 4.2.2. Equipment ..............................................................................................................64 4.2.3. Column evaluation.................................................................................................65 4.2.4. Calculations............................................................................................................65 4.3. Results and Discussion .................................................................................................65 4.3.1. Performance of the chiral stationary phases ..........................................................65 4.3.2. Effect of mobile phase composition.......................................................................66 iv 4.3.3. Effects of the structure of the analyte ....................................................................67