Abstract
Gas chromatography‐mass spectrometry (GC‐MS) with supersonic molecular beams (SMBs) (also named Supersonic GC‐MS) is based on GC and MS interface with SMBs and on the electron ionization (EI) of vibrationally cold analytes in the SMBs (cold EI) in a fly‐through ion source. This ion source is inherently inert and further characterized by fast response and vacuum background filtration capability. The same ion source offers three modes of ionization including cold EI, classical EI and cluster chemical ionization (CI). Cold EI, as a main mode, provides enhanced molecular ions combined with an effective library sample identification, which is supplemented and complemented by a powerful isotope abundance analysis method and software. The range of low‐volatility and thermally labile compounds amenable for analysis is significantly increased owing to the use of the contact‐free, fly‐through ion source and the ability to lower sample elution temperatures through the use of high column carrier gas flow rates. Effective, fast GC‐MS is enabled particularly owing to the possible use of high column flow rates and improved system selectivity in view of the enhancement of the molecular ion. This fast GC‐MS with SMB can be further improved via the added selectivity of MS‐MS, which by itself benefits from the enhancement of the molecular ion, the most suitable parent ion for MS‐MS. Supersonic GC‐MS is characterized by low limits of detection (LOD), and its sensitivity is superior to that of standard GC‐MS, particularly for samples that are hard for analysis. The GC separation of the Supersonic GC‐MS can be improved with pulsed flow modulation (PFM) GC × GC‐MS. Electron ionization LC‐MS with SMB can also be combined with the Supersonic GC‐MS, with fast and easy switching between these two modes of operation. Copyright © 2008 John Wiley & Sons, Ltd.