Uniformity and Sensitivity Improvements in Comprehensive Two-Dimensional Gas Chromatography Using Flame Ionization Detection with Post-Column Reaction.

A 3D-printed microreactor for post-column reactions was successfully integrated with comprehensive two -dimensional  gas chromatography. A two-stage post-column reaction provided a carbon-independent response, enhanced the flame ionization detection uniformity, and improved the detector sensitivity. These enhancements are critical to overcome challenges in analyses using comprehensive two-dimensional gas chromatography and flame ionization detection, which aim to separate and quantify multiple components. Post-column reaction flame ionization detection eliminated the requirement of multilevel and multicompound calibration, it enabled the determination of target analytes with a single-carbon-containing calibration compound with an accuracy of ±10%, and it improved the sensitivity for compounds that were not efficiently ionized by flame ionization detection. Extra column band-broadening caused by the incorporation of the 3D-printed microreactor was minimized using optimized reactor operating parameters and intercolumn connectivity. Chromatographic fidelity was in the practical domain of comprehensive 2D gas chromatography. Typical peak widths at half-height using the described approach ranged from 165 to 235 ms for probe compounds with retention factors spanning 5 < k < 40.