Quantitative relationship between structure and retention in reversed-phase HPLC: an extended incremental approach to predict triacylglycerines retention
Abstract
Based on the analysis of literature data on the properties of grafted reversed phases and the structure
of n-alkanes in the solid state, it is assumed that n-alkyl substituents of sorbate molecules as well as substituents with trans-alkenyl moieties can easily penetrate the grafted layer. However, the cis-double C=C-bond in the n-alkenyl substituents the process is hindered for steric reasons, hence the farther from the end of alkenyl substituent is the double bond located the greater is its retention. This explains the features of sorption of sorbates with n-alkyl and n-alkenyl substituents in reversed-phase chromatography. It is shown that the incremental approach based on the features of the sorption of triacylglycerines with higher fatty acid substituents of different plan seed oils can be extended to the retention of substances with isomeric substituents (by the position of the double bond in the carbon chain) radicals in the composition of triacylglycerols of fatty acids. This was proved by effective prediction of retention of carrot seeds triacylglycerols formed by petroselinic acid (6Z-octadececenoic), as isomers of oleic (9Z-octadececenoic) taking into account the difference of logarithms of retention factor difference for internal and external (relative to the double bond) CH2-group addition. The latter was calculated for a special set of increments for triacylglycerides with substituents of 11Z-eicosenoic and erucic (13Z-docosaenoic) acids vs that for pait of palmitic and stearic acids. The procedure was repeated for unique seed oil Limnantes alba, composed by specific uncommon fatty acid substituents.
The procedure was applied to solute retention in reversed-phase HPLC.
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