Retrieval of structure information from retention index.
The chromatographic identity of a compound can be determined by four parameters, namely, I, A, Z and (GRF). These are interrelated in a linear regression equation, given in the paper as Eq. 8. The retrieval of structural information from retention data requires the introduction of a new meaning to the Kováts retention index, the use of column difference (delta I) to characterize functional groups, the redefinition of the role of electronegative oxygen and nitrogen atoms, and the division of retention index (I) into contributions from atoms and from functional groups. The separation of retention index (I) into molecular and interaction contributions is a necessary condition for retention index prediction from structure and also for structure information retrieval from retention data. According to Eq. 8 the retention index is uniquely determined by three parameters, namely A, Z and (GRF). For prediction of retention index, the A value is assigned a value of 100 index units (i.u.), the Z value is obtained directly from the compound, and the (GRF) value is pre-calibrated. In Eq. 10, the m and n values represent the pre-calibrated terms for a quantitative structure-retention index relationship. These terms account for the positive and negative retention contributions from polar and polarizable atom groups. All atom groups that are different from methylene and methyl groups will interact with the stationary phase and contribute to retention. The m and n values for various functional, polar and polarizable atom groups and their column differences (delta I values) are the results of interactions between the solute and the stationary phase and are structure dependent. The interaction increases with increasing polarities of the solute and the stationary phase. The column difference not only reflects the strength of the interaction, but is also characteristic of the functional and polarizable groups. The retrieval of structural information from retention data is equivalent to obtaining Z and (GRF) values from known I and delta I values, which is straightforward for monofunctional compounds. For multi-functional compounds, additional data will be needed for retrieval of structural information. These can be obtained from derivatization of the unknown compound, from its chemical reactions with other reagents, from GC-MS analysis and from structure match using internal or external standards. The additional data required will depend upon the complexity of the unknown structure. This approach demonstrates that a system can be devised to utilize GC retention characteristics uniquely for structure elucidation.
Department of Pharmaceutical Chemistry, School of Pharmacy, University of California, San Francisco 94143-0446.
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Peng
D002627:Chemistry, Physical / Q000295:instrumentation* / Q000592:standards; D002845:Chromatography; D006801:Humans; D015394:Molecular Structure