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Use of Surfactant Modifiers for High-Performance Liquid Chromatography of Aliphatic and Aromatic Acids and Capillary Electrophoresis of Glycosaminoglycans

Fasciano, Jennifer Marie
http://orcid.org/0000-0001-7740-7149
http://rave.ohiolink.edu/etdc/view?acc_num=miami1448126648

Abstract Details

2015, Doctor of Philosophy, Miami University, Chemistry and Biochemistry.
Separations of short chain carboxylic acids by ion exclusion chromatography (IELC) are typically performed on strong cation exchange columns under standard HPLC conditions but not in the ultra-HPLC (UHPLC) mode. A novel IELC method for the efficient separation of short chain carboxylic acids by either HPLC or UHPLC utilizing a C18 column dynamically modified with sodium dodecyl sulfate (SDS) has been developed. Under optimized conditions, a HPLC separation of four aliphatic carboxylic acids such as tartaric, malonic, lactic, and acetic can be achieved in under four minutes at 0.6 mL/min, and in less than two minutes in the UHPLC mode at 2.1 mL/min. Column lifetime could be monitored by the quality of the fumaric and maleic acid separation. The separation of hydroxybenzoic acid positional isomer mixtures was studied by micellar liquid chromatography (MLC) using sodium dodecylsulfate (SDS) as the modifying surfactant on a C18 UHPLC column. The addition of only SDS (no organic solvent) to the mobile phase reduced the influence of hydrophobic interactions while improving the separation efficiency, even at concentrations below the critical micellization concentration (CMC). Under optimized conditions, a UHPLC separation of seven di- and tri-hydroxybenzoic acids can be achieved in under six minutes, and a mixture of six monohydroxybenzoic acid isomers can be separated in less than twenty minutes at 0.3 mL/min. Solute-micelle equilibrium constants and partition coefficients were calculated for monohydroxybenzoic acids and were classified as binding solutes in the MLC retention mechanism. After trying shorter chain surfactants, it was concluded that increasing chain length led to more efficient MLC separations, but SDS is the preferred modifying surfactant for the examined separation. The global crisis resulting from adulterated heparin in late 2007 and early 2008 revived the importance of improved analytical techniques for purity analysis of heparin products. The separation of heparin and heparin-like compounds was studied by capillary electrophoresis (CE) with indirect UV detection. Naphthalene sulfonates were used as detection agents, shifting the detection wavelength into the upper UV range. Naphthalene disulfonate was found to be the most effective detection agent for the qualitative analysis of heparin and heparin-like compounds. The synthetic contaminant, over-sulfated chondroitin sulfate (OSCS), was observed as a unique positive peak in the electropherograms.
Neil Danielson, Ph.D. (Advisor)
Jon Scaffidi, Ph.D. (Committee Chair)
Richard Taylor, Ph.D. (Committee Member)
Andre Sommer, Ph.D. (Committee Member)
Douglas Coffin, Ph.D. (Committee Member)
182 p.
Analytical Chemistry; Chemistry
Glycosaminoglycans; Heparin; Ion Chromatography; Ion Exclusion Liquid Chromatography; Micellar Liquid Chromatography; Ultra-High Performance Liquid Chromatography

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Citations

  • Fasciano, J. M. (2015). Use of Surfactant Modifiers for High-Performance Liquid Chromatography of Aliphatic and Aromatic Acids and Capillary Electrophoresis of Glycosaminoglycans [Doctoral dissertation, Miami University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=miami1448126648

    APA Style (7th edition)

  • Fasciano, Jennifer. Use of Surfactant Modifiers for High-Performance Liquid Chromatography of Aliphatic and Aromatic Acids and Capillary Electrophoresis of Glycosaminoglycans. 2015. Miami University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=miami1448126648.

    MLA Style (8th edition)

  • Fasciano, Jennifer. "Use of Surfactant Modifiers for High-Performance Liquid Chromatography of Aliphatic and Aromatic Acids and Capillary Electrophoresis of Glycosaminoglycans." Doctoral dissertation, Miami University, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=miami1448126648

    Chicago Manual of Style (17th edition)

miami1448126648
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© 2015, all rights reserved.
This open access ETD is published by Miami University and OhioLINK.