title: Trilinearity deviation ratio: a new metric for chemometric analysis of comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry data.
abstract: Comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) is a well-established instrumental platform for complex samples. However, chemometric data analysis is often required to fully extract useful information from the data. We demonstrate that retention time shifting from one modulation to the next, Δ(2)tR, is not sufficient alone to quantitatively describe the trilinearity of a single GC×GC-TOFMS run for the purpose of predicting the performance of the chemometric method parallel factor analysis (PARAFAC). We hypothesize that analyte peak width on second dimension separations, (2)Wb, also impacts trilinearity, along with Δ(2)tR. The term trilinearity deviation ratio, TDR, which is Δ(2)tR normalized by (2)Wb, is introduced as a quantitative metric to assess accuracy for PARAFAC of a GC×GC-TOFMS data cube. We explore how modulation ratio, MR, modulation period, PM, temperature programming rate, Tramp, sampling phase (in-phase and out-of-phase), and signal-to-noise ratio, S/N, all play a role in PARAFAC performance in the context of TDR. Use of a PM in the 1-2 s range provides an optimized peak capacity for the first dimension separation (500-600) for a 30 min run, with an adequate peak capacity for the second dimension separation (12-15), concurrent with an optimized two-dimensional peak capacity (6000-7500), combined with sufficiently low TDR values (0-0.05) to facilitate low quantitative errors with PARAFAC (0-0.5%). In contrast, use of a PM in the 5s or greater range provides a higher peak capacity on the second dimension (30-35), concurrent with a lower peak capacity on the first dimension (100-150) for a 30 min run, and a slightly reduced two-dimensional peak capacity (3000-4500), and furthermore, the data are not sufficiently trilinear for the more retained second dimension peaks in order to directly use PARAFAC with confidence.
authors.affiliation: Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195-1700, USA.
authors.forename: David K
authors.initials: DK
authors.lastname: Pinkerton
authors.affiliation: Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195-1700, USA.
authors.forename: Brendon A
authors.initials: BA
authors.lastname: Parsons
authors.affiliation: Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195-1700, USA.
authors.forename: Todd J
authors.initials: TJ
authors.lastname: Anderson
authors.affiliation: Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195-1700, USA. Electronic address: synovec@chem.washington.edu.
authors.forename: Robert E
authors.initials: RE
authors.lastname: Synovec
keywords: Chemometrics; GC×GC–TOFMS; PARAFAC; Peak capacity; Trilinearity