Absolute Configuration of Aliphatic Hydrocarbon Enantiomers Identified by Gas Chromatography: Theorized Application for Isoprenoid Alkanes and the Search of Molecular Biosignatures on Mars

Abstract

Acyclic saturated hydrocarbon enantiomers were resolved by gas chromatography using a β-cyclodextrin-based chiral stationary phase. The stereospecific synthesis of single enantiomers of 4-methyloctane allowed to assign the absolute stereochemical configuration to the resolved enantiomers. Data show that the (S)-4-methyloctane shows higher chromatographic retention as compared to the (R)-4-methyloctane due to stronger van der Waals interactions with the β-cyclodextrin chiral selector. This introductive research presents future prospects for the separation of stereoisomers of larger branched hydrocarbons. We discuss the importance of chiral hydrocarbons, more precisely the stereochemistry of the isoprenoid alkanes pristane and phytane, as potential biosignatures stable on geological timescales. The origins of pristane and phytane in Earth sediments are presented, and we detail the implications for the search of extinct or extant life on Mars. The data presented here will help to systematically investigate the chirality of hydrocarbon enantiomers in biological and nonbiological samples and in samples to be analyzed by the ESA’s ExoMars rover to trace the chiral precursors of life in 2023.

Keywords

• alkanes
• chirality
• cyclodextrin
• ExoMars
• gas chromatography
• isoprenoids