Analytical and Bioanalytical Chemistry

, Volume 405, Issue 30, pp 9879–9888 | Cite as

Relationship between the matrix effect and the physicochemical properties of analytes in gas chromatography

  • Kanju SakaEmail author
  • Keiko Kudo
  • Makiko Hayashida
  • Emiko Kurisaki
  • Hisae Niitsu
  • Masaru Terada
  • Koji Yamaguchi
  • Ken-ichi Yoshida
Research Paper


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.


Matrix effect Gas chromatography Quantitative structure–property relationship H-bond donor 



This study was supported by the Japan Society for the Promotion of Science KAKENHI Grant Numbers 24590850, 24659338. The authors would like to thank Kohtaro Yuta (In Silico Data, Japan), Masato Kitajima, and Jose M. Ciloy (Fujitsu Kyushu Systems Ltd., Japan) for their helpful discussions and valuable comments on the manuscript.


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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Kanju Saka
    • 1
    Email author
  • Keiko Kudo
    • 2
  • Makiko Hayashida
    • 3
  • Emiko Kurisaki
    • 4
  • Hisae Niitsu
    • 5
  • Masaru Terada
    • 6
  • Koji Yamaguchi
    • 3
  • Ken-ichi Yoshida
    • 1
  1. 1.Department of Forensic Medicine, Graduate School of MedicineUniversity of TokyoTokyoJapan
  2. 2.Department of Forensic Pathology and Sciences, Graduate School of Medical SciencesKyushu UniversityFukuokaJapan
  3. 3.Department of Legal Medicine, Graduate School of MedicineNippon Medical SchoolTokyoJapan
  4. 4.Department of Legal MedicineFukushima Medical University School of MedicineFukushimaJapan
  5. 5.Department of Legal MedicineIwate Medical University School of MedicineShiwa-gunJapan
  6. 6.Department of Legal MedicineToho University School of MedicineTokyoJapan

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