Performance and selectivity of amphiphilic pillar[5]arene as stationary phase for capillary gas chromatography

Pillar[n]arenes possess highly symmetrical and rigid pillar-shaped architecture with π-electron rich cavity that afford their reliable host-guest recognition interactions towards matched guests. In this work, a novel amphiphilic pillar[5]arene (P5A-C10-2NH₂) was designed, synthesized and employed as the stationary phase for capillary gas chromatography. To date, they have not been reported in the field of chromatography. The P5A-C10-2NH₂ capillary column (10 m × 0.25 mm i.d.) was prepared by static coating method. Its capillary column exhibited moderate polarity and column efficiency of 2265 plates/m determined by naphthalene at 120 °C. As evidenced, the P5A-C10-2NH₂ column achieved advantageous separation performance for a mixture of 24 analytes of diverse types and exhibited different chromatographic selectivity from two pillar[5]arene derivatives columns and commercial HP-35 column with 35%-phenyl-methylpolysiloxane. Moreover, the P5A-C10-2NH₂ column baseline resolved more than a dozen positional and cis-trans isomers. Furthermore, the separation mechanism of P5A-C10-2NH₂ column was discussed by quantum chemical calculations. In addition, the P5A-C10-2NH₂ column had high thermal stability and excellent separation repeatability 0.01-0.04% for run-to-run, 0.03-0.17% for day-to-day and 3.2-3.9% for column-to-column. The special amphiphilic structure and high resolution for various analytes reveal the good potential of pillararenes as a new class of stationary phases for chromatographic analyses. Moreover, the TPG column achieved improved thermal stability over the GIL column and excellent repeatability.