Sensitive determination of thiols in wine samples by a stable isotope-coded derivatization reagent d0/d4-acridone-10-ethyl-N-maleimide coupled with high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry analysis

J Chromatogr A. 2017 Mar 31:1491:98-107. doi: 10.1016/j.chroma.2017.02.042. Epub 2017 Feb 24.

Abstract

As the key aroma compounds, varietal thiols are the crucial odorants responsible for the flavor of wines. Quantitative analysis of thiols can provide crucial information for the aroma profiles of different wine styles. In this study, a rapid and sensitive method for the simultaneous determination of six thiols in wine using d0/d4-acridone-10-ethyl-N-maleimide (d0/d4-AENM) as stable isotope-coded derivatization reagent (SICD) by high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) has been developed. Quantification of thiols was performed by using d4-AENM labeled thiols as the internal standards (IS), followed by stable isotope dilution HPLC-ESI-MS/MS analysis. The AENM derivatization combined with multiple reactions monitoring (MRM) not only allowed trace analysis of thiols due to the extremely high sensitivity, but also efficiently corrected the matrix effects during HPLC-MS/MS and the fluctuation in MS/MS signal intensity due to instrument. The obtained internal standard calibration curves for six thiols were linear over the range of 25-10,000pmol/L (R2≥0.9961). Detection limits (LODs) for most of analytes were below 6.3pmol/L. The proposed method was successfully applied for the simultaneous determination of six kinds of thiols in wine samples with precisions ≤3.5% and recoveries ≥78.1%. In conclusion, the developed method is expected to be a promising tool for detection of trace thiols in wine and also in other complex matrix.

Keywords: HPLC-ESI-MS/MS; Stable isotope-coded derivatization (SICD); Thiols; Wine.

MeSH terms

  • Chromatography, High Pressure Liquid / methods*
  • Isotope Labeling
  • Maleimides / chemistry*
  • Spectrometry, Mass, Electrospray Ionization / methods*
  • Sulfhydryl Compounds / analysis*
  • Tandem Mass Spectrometry / methods
  • Wine / analysis*

Substances

  • Maleimides
  • Sulfhydryl Compounds