title: Extension of the two-dimensional mass channel cluster plot method to fast separations utilizing low thermal mass gas chromatography with time-of-flight mass spectrometry.
abstract: Implementation of a data reduction and visualization method for use with high-speed gas chromatography and time-of-flight mass spectrometry (GC-TOFMS) is reported. The method, called the "2D m/z cluster method" facilitates analyte detection, deconvolution, and identification, by accurately measuring peak widths and retention times using a fast TOFMS sampling frequency (500 Hz). Characteristics and requirements for high speed GC are taken into consideration: fast separations with narrow peak widths and high peak capacity, rapid data collection rate, and effective peak deconvolution. Transitioning from standard GC (10-60+ minute separations) to fast GC (1-10 min separations) required consideration of how to properly analyze the data. This report validates use of the 2D m/z cluster method with newly developed GC technology that produces ultra-fast separations (∼1 min) with narrow analyte peak widths. Low thermal mass gas chromatography (LTM-GC) operated at a heating rate of 250 °C/min coupled to a LECO Pegasus III TOFMS analyzed a 115 component test mixture in 120 s with peak widths-at-base, wb (4σ), of 350 ms (average) to produce a separation with a high peak capacity, nc ∼ 340 (at unit resolution Rs = 1). The 2D m/z cluster method is shown to separate overlapped analytes to a limiting Rs ∼ 0.03, so the effective peak capacity was increased nearly 30-fold to nc ∼10,000 in the 120 s separation. The method, when coupled with LTM-GC-TOFMS, is demonstrated to provide unambiguous peak rank (i.e. the number of analytes per overlapped peak in the total ion current (TIC)), by visualizing locations of pure and chromatographically overlapped m/z. Hence, peak deconvolution and identification using MCR-ALS (multivariate curve resolution - alternating least squares) is demonstrated.
authors.affiliation: Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195, USA.
authors.forename: Brian D
authors.initials: BD
authors.lastname: Fitz
authors.affiliation: Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195, USA. Electronic address: synovec@chem.washington.edu.
authors.forename: Robert E
authors.initials: RE
authors.lastname: Synovec
keywords: Chemometric data analysis; Gas chromatography; Low thermal mass (LTM); Peak capacity; TOFMS