title: The chemometric resolution and quantification of overlapped peaks form comprehensive two-dimensional liquid chromatography.
abstract: The chemometric resolution and quantification of overlapped peaks from comprehensive two-dimensional (2D) liquid chromatography (LCxLC) data are demonstrated. The LCxLC data is produced from an in-house LCxLC analyzer that couples an anion-exchange column via a multi-port valve with a reversed-phase column connected to a UV absorbance detector. Three test mixtures, each containing a target analyte, are subjected to partial LCxLC separations to simulate likely cases of signal overlap. The resulting unresolved target-analyte signals are then analyzed by the standard-addition method and two chemometric methods. The LCxLC analyses of a test mixture and its corresponding standard-addition mixture results in two data matrices, one for each mixture. The stacking of these two data matrices produces a data structure that can then be analyzed by trilinear chemometric methods. One method, the generalized rank annihilation method (GRAM), uses a non-iterative eigenvalue-based approach to mathematically resolve overlapped trilinear signals. The other method, parallel factor analysis (PARAFAC), uses an iterative approach to resolve trilinear signals by the optimization of initial estimates using alternating least squares and signal constraints. In this paper, GRAM followed by PARAFAC analysis is shown to produce better qualitative and quantitative results than using each method separately. For instance, for all three test mixtures, the GRAM-PARAFAC approach improved quantitative accuracy by at least a factor of 4 and quantitative precision by more than 2 when compared to GRAM alone. This paper also introduces a new means of correcting run-to-run retention time shifts in comprehensive 2D chromatographic data.
authors.affiliation: Department of Chemistry, 2355 Fairchild Dr., Suite 2N225, United States Air Force Academy, CO 80840-6230, USA. carlos.fraga@usafa.af.mil
authors.forename: Carlos G
authors.initials: CG
authors.lastname: Fraga
authors.forename: Cynthia A
authors.initials: CA
authors.lastname: Corley
mesh_terms: D019817:Benzoic Acid / Q000302:isolation & purification; D005591:Chemical Fractionation / Q000379:methods*; D002723:Chlorobenzoates / Q000302:isolation & purification; D002852:Chromatography, Ion Exchange / Q000379:methods; D002853:Chromatography, Liquid / Q000295:instrumentation / Q000379:methods*; D005163:Factor Analysis, Statistical; D005650:Fumarates / Q000302:isolation & purification; D008298:Maleates / Q000302:isolation & purification; D009943:Organophosphorus Compounds / Q000302:isolation & purification; D019289:Pyruvic Acid / Q000302:isolation & purification; D014498:Uracil / Q000302:isolation & purification
chemical_list: D002723:Chlorobenzoates; D005650:Fumarates; D008298:Maleates; D009943:Organophosphorus Compounds; D014498:Uracil; D019289:Pyruvic Acid; C032005:fumaric acid; D019817:Benzoic Acid; C030272:maleic acid; C040768:4-chlorobenzoic acid