Unlocking New Capabilities in the Analysis of GC × GC-TOFMS Data With Shift-Invariant Multi-Linearity

Abstract

This paper introduces a novel deconvolution algorithm, shift-invariant multi-linearity (SIML), which significantly enhances the analysis of data from two-dimensional gas chromatography instruments coupled to a time-of-flight mass spectrometer (GC × GC-TOFMS). Designed to address the challenges posed by retention time shifts and high noise levels, SIML incorporates wavelet-based smoothing and Fourier-transform based shift-correction within the multivariate curve resolution-alternating least squares (MCR-ALS) framework. We benchmarked the SIML algorithm against non-negativity constrained MCR-ALS and parallel factor analysis 2 with flexible coupling (PARAFAC2 × N) using both simulated and real GC × GC-TOFMS datasets. Our results demonstrate that SIML provides unique solutions with significantly improved robustness, particularly in low signal-to-noise ratio scenarios, where it maintains high accuracy in estimating mass spectra and concentrations. The enhanced reliability of quantitative analyses afforded by SIML underscores its potential for broad application in complex matrix analyses across environmental science, food science, and biological research.