Amphiphilic calix[4]arenes as a highly selective gas chromatographic stationary phase for aromatic amine isomers

Abstract

Efficient separation of aromatic amine isomers is a challenging issue in chemical industry and environmental analysis. Here we report the use of p-amino-tetradecyloxy-calix[4]arene (C4A-NH₂) as a novel stationary phase for gas chromatographic (GC) separations. The statically coated C4A-NH₂ capillary column showed a high column efficiency of 4332 plates/m for a 0.25 mm ID column and medium polarity. The C4A-NH₂ stationary phase exhibited an excellent separation performance both for aromatic amine isomers and a complex mixture of aliphatic analytes with a wide ranging polarity, showing distinct advantages over the commercial polysiloxane stationary phases via diversified molecular interactions covering H-bonding, π-π, van der Waals interactions and shape-fitting selectivity. The retention mechanisms of aromatic amine isomers on C4A-NH₂ column were further investigated by quantum chemistry calculations. In addition, the C4A-NH₂ column showed good column repeatability with relative standard deviation (RSD) values of 0.03%-0.07% for run-to-run, 0.10%-0.27% for day-to-day and 2.6%-5.7% for column-to-column, respectively, and thermal stability up to 240℃.

Keywords: Aromatic amine isomers; Calix[4]arene; Gas chromatography; Quantum chemistry calculations; Separation performance.