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Quantification of coumarin in cinnamon and woodruff beverages using DIP-APCI-MS and LC-MS

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Abstract

The use of the direct inlet probe–atmospheric-pressure chemical ionization (DIP-APCI) ion source developed in our laboratory coupled to a high resolution Q-TOF MS for the quantitative analysis of coumarin in different cinnamon samples was demonstrated in this study. Extraction of coumarin from various cinnamon samples was followed by DIP-APCI-mass spectrometry (MS) and liquid chromatography (LC)-MS analysis. For quantification, an external calibration with and without the use of stable isotope-labeled coumarin as internal standard was compared. The results obtained by DIP-APCI-MS and LC-MS were in good agreement. Even without the use of an internal standard satisfying linearity (R 2 > 0.997), recovery (94–104 % for spiking levels between 100 and 5,000 mg/kg) and intra- and interday repeatability (2.2–13.8 %RSD) was demonstrated using DIP-APCI-MS. To reduce the number of samples requiring quantitative analysis, the possibility of semi-quantitative screening of coumarin directly from powdered cinnamon using DIP-APCI-MS was shown. The analysis of woodruff-flavored beverages and cinnamon-flavored chewing gum by DIP-APCI-MS resulted in the formation of an artifact interfering with coumarin detection. As with other ambient ionization methods, special attention has to be paid to possible spectral interferences due to isobaric substances present in the sample matrix or formed from matrix components after ionization. The temperature-programmed vaporization in DIP-APCI-MS combined with the use of stable isotope-labeled coumarin as internal standard helped in recognizing this interference.

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Acknowledgment

The authors thank Scientific Instruments Manufacturer GmbH (SIM) for providing the direct inlet probe and Phenomenex Inc. for providing the Kinetex column. Sonja Krieger also thanks the Zentrum fuer Graduiertenstudien of the University of Wuppertal for funding.

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Authors and Affiliations

  1. Institute for Pure and Applied Mass Spectrometry, University of Wuppertal, Gauss-Str. 20, 42119, Wuppertal, Germany

    Sonja Krieger & Oliver J. Schmitz

  2. Applied Analytical Chemistry, University of Duisburg-Essen, Universitaetsstr 5-7, 45141, Essen, Germany

    Sonja Krieger & Oliver J. Schmitz

  3. Department of Food Chemistry, University of Wuppertal, Gauss-Str. 20, 42119, Wuppertal, Germany

    Heiko Hayen

Authors
  1. Sonja Krieger
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  2. Heiko Hayen
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  3. Oliver J. Schmitz
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Correspondence to Oliver J. Schmitz.

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Krieger, S., Hayen, H. & Schmitz, O.J. Quantification of coumarin in cinnamon and woodruff beverages using DIP-APCI-MS and LC-MS. Anal Bioanal Chem 405, 8337–8345 (2013). https://doi.org/10.1007/s00216-013-7238-x

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  • DOI: https://doi.org/10.1007/s00216-013-7238-x

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