High temperature gas chromatography-time-of-flight-mass spectrometry (HTGC-ToF-MS) for high-boiling compounds.

High temperature gas chromatography (HTGC) is a routine technique for the analysis of high boiling compounds which are eluted from the column with oven cycling up to > 400 °C. In contrast, the coupling of HTGC with mass spectrometry (HTGC-MS) has received relatively little attention. This may be due to the availability of GC columns, mass spectrometers and accessories that are able to withstand constant high temperature cycling. We have assembled a HTGC-time of flight-MS (HTGC-ToF-MS) system from readily available products that is capable of rapid (<25 min) analysis of ∼C₁₀₋₁₀₀ hydrocarbon boiling equivalents and full mass spectral data recording up to m/z 1850. Here we report initial results from the analysis of diverse substrates including:long-chain (> C₆₀) n-alkanes, n-acid methyl esters up to C₆₄, triacylglycerides (TAGs) with molecular and fragment ions in a single analysis, intact wax esters from C₄₀₋₆₄, C₈₀ glycerol alkyl glycerol tetraethers (GDGTs), and C₃₃₋₄₄ metallated porphyrins. Mass spectrometry at 430 °C was achievable on a routine basis without significant thermal degradation of analytes. The method is applicable to analysis of a wide range of industrial, environmental, biological, geochemical and other samples where high molecular weight analytes are of interest.