The competition between two molecules of similar polarity for adsorption sites on the stationary phase is discussed in light of rapid kinetics of adsorption and desorption, and of the effects of temperature, acetonitrile, surfactant (cyclohexylaminopropane sulfonic acid, CAPS) and salt concentrations on the retention of the thyroid hormones (3,5-diiodothyronine, T2; 3,3',5-triiodothyronine, T3 and thyroxine, T4). A three parameter equation relates the surfactant concentration and ionic strength to the retention of the hormones and is analyzed in terms of the Stern-Gouy-Chapman theory. A second order polynomial describes the temperature dependency and permits the evaluation of the enthalpy, entropy and heat capacity, demonstrating a reduction in the molecular motion of the analyte with increasing surfactant and acetonitrile concentrations. The equation parameters for linear or non-linear equations, using data sets with or without homogeneous variances, are evaluated using a Simplex optimization procedure that uses one of two proposed optimization criteria. The construction and operation of a computer based gradient programmer for HPLC is described. A surfactant mediated gradient elution with electrochemical detection is examined for the analysis of serum thyroid hormones.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.72024 |
| Date | January 1985 |
| Creators | Bedard, Pierre R. |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Master of Science (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 000227248, proquestno: AAINL24018, Theses scanned by UMI/ProQuest. |
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