A series-coupled ensemble of two capillary GC columns of different selectivity with an adjustable pressure at the column junction point is used to obtain tunable selectivity for high-speed GC and GC/TOFMS. An electronic pressure controller with a 0.1-psi step size is used to obtain numerous computer-selected unique selectivities. System configurations for conventional, atmospheric-pressure outlet operation with flame ionization detection and for vacuum-outlet operation with photoionization detection are described for GC-only experiments. Polydimethylsiloxane is used as the non-polar column and polyethylene glycol (atmospheric outlet) or triflouropropylpolysiloxane (vacuum outlet) is used as the polar column. For GC/TOFMS experiments, 5% phenyl polydimethylsiloxane was used as the non-polar column, and polyethylene glycol was used as the polar column. The time-of-flight mass spectrometer can acquire up to 500 complete mass spectra per second. Since spectral continuity is achieved across the entire chromatographic peak profile, severely overlapping peaks can be spectrally deconvoluted for high-speed characterization of completely unknown mixtures. For mixture components with significantly different fragmentation patterns, spectral deconvolution can be achieved for chromatographic peak separations of as little as 6.0 ms. This can result is very large peak capacity for time compressed (not completely resolved) chromatograms. The use of columns with tunable selectivity allows for precise peak-position control, which can result in more efficient utilization of available peak capacity and thus further time compression of chromatograms. The limits of tunability and deconvolution are tested for near co-elutions of different classes of hydrocarbon compounds as well as for more multi-functional mixtures.
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