title: Relationship between the matrix effect and the physicochemical properties of analytes in gas chromatography.
abstract: The phenomenon "matrix-induced chromatographic response enhancement" (matrix effect) causes quantitative errors in gas chromatography (GC) analyses. This effect varies according to the analyte nature, matrix type and concentration, and GC-system parameters. By focusing on the physicochemical properties of analytes, a predictive model was developed for the matrix effect using quantitative structure-property relationships. Experimental values of the matrix effect were determined for 58 compounds in a serum extract obtained from solid-phase extraction as the matrix. Eight molecular descriptors were selected, and the matrix-effect model was developed by multiple linear regression. The developed model predicted values for the matrix effect without any further experimental measurements. It also indicated that the molecular polarity (particularly H-bond donors) and volume of the analyte increase the matrix effect, while hydrophobicity and increasing number of nonpolar carbon atoms in the analyte decrease the matrix effect. The model was applied to the analysis of barbiturates. The predicted values indicated that N-methylation decreases the matrix effect, and the relative predicted values were effective for the selection of an internal standard. The obtained insight into the matrix effect and the prediction data will be helpful for developing quantitative analysis strategies.
authors.affiliation: Department of Forensic Medicine, Graduate School of Medicine, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan, kanju@m.u-tokyo.ac.jp.
authors.forename: Kanju
authors.initials: K
authors.lastname: Saka
authors.forename: Keiko
authors.initials: K
authors.lastname: Kudo
authors.forename: Makiko
authors.initials: M
authors.lastname: Hayashida
authors.forename: Emiko
authors.initials: E
authors.lastname: Kurisaki
authors.forename: Hisae
authors.initials: H
authors.lastname: Niitsu
authors.forename: Masaru
authors.initials: M
authors.lastname: Terada
authors.forename: Koji
authors.initials: K
authors.lastname: Yamaguchi
authors.forename: Ken-ichi
authors.initials: K
authors.lastname: Yoshida
mesh_terms: D002784:Cholesterol / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006801:Humans; D057927:Hydrophobic and Hydrophilic Interactions; D004364:Pharmaceutical Preparations / Q000097:blood*; D021281:Quantitative Structure-Activity Relationship; D052616:Solid Phase Extraction
chemical_list: D004364:Pharmaceutical Preparations; D002784:Cholesterol