Novel HPLC separation methodologies compatible with chemiluminescent nitrogen detection

The methodology of high performance liquid chromatography (HPLC) separations has been well established through the research of the past few decades. Protocols have been established for conducting separations of specific classes of compounds and are widely used. This has in a fashion hindered the development of HPLC. Without challenging previous approaches and continuing to rely on past experiences new advances are not common place.;The advent of the commercial chemiluminescent nitrogen detector (CLND) has forced researchers to re-examine the approaches which have been employed for years. The CLND was developed with the pharmaceutical market in mind, providing a detector that can offer universal response to any nitrogen containing compound, regardless of the presence or absence of chromophores. This benefit however comes with a challenge: the eluent cannot contain any nitrogen species.;Pushing this detector beyond the initial vision of those who built it provides a powerful new tool for the analytical chemist, if the separations can be accomplished without nitrogen. The first part of the thesis will deal with the adaptation of current techniques in reverse phase, ion exchange and ion-pair chromatography for use with CLND. The reversed phase separation of cationic and zwitterionic surfactants required the use of barium to block amine-silanol interactions. Ion exchange chromatography illustrated the ability of the CLND to do analysis with a complex matrix under high salt conditions. Ion-pair chromatography of anionic metal-cyanide complexes posed the greatest challenge, requiring the use of a phosphonium cation instead of an ammonium cation as the ion-pairing agent. This led to the developments explored in the final portion of the thesis: the comparison of ion-pairing characteristics of ammonium, phosphonium and sulfonium cations. The three classes of cation showed significant differences in their selectivities towards several different classes of anions. These differences in retention lead to the beginnings of a potential model on the nature of ion retention in ion pair chromatography.