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

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.

Structure–activity relationship studies of 4-methylcoumarin derivatives as anticancer agents

“…They are present at high levels in cinnamon and many fruits and vegetables (Krieger et al, 2013;Ribeiro da Silva et al, 2014). Different derivatives of these compounds possess a wide range of biological activities (Venugopala et al, 2013) such as antioxidant (Morabito et al, 2010;Natella et al, 2010;Pedersen et al, 2007), anti-inflammatory (Togna et al, 2014), antimicrobial (Gupta et al, 2012), and in vitro (Macakova et al, 2012) and in vivo platelet anti-aggregation effects .…”

2-Oxoglutarate-dependent dioxygenases in the biosynthesis of simple coumarins

“…Plant researchers consider coumarins as a potential fluorescent and flavoring component (Poulton et al, 1980; Oba et al, 1981; Mock et al, 1999; Katerinopoulos, 2004; Bourgaud et al, 2006; Stanfill et al, 2007; Maggi et al, 2011; Krieger et al, 2013). Tracer experiments using cinnamate ( 10 ) or its derivatives have effectively shown that simple coumarin formation in plants proceeds via hydroxylation of the ortho -position ( ortho -hydroxylation) of respective cinnamates, the adjacent position in the benzene ring to the side chain (Brown et al, 1960; Brown, 1962; Fritig et al, 1970; Bayoumi et al, 2008a), followed by formation of a lactone ring.…”

Quantitative Analysis of Bisphenol A in Recycled Paper with a Novel Direct Inlet Probe-Atmospheric Pressure Photoionization–IonTrap-MS

“…Furthermore, limits of detection (LOD), limits of quantification (LOQ) and coefficient of determination (R 2 ) were calculated and listed in Table 1. For comparison the values determined by Krieger et al [13] for the DIP-APCI are added and show that comparable values for LOD and LOQ are obtained with DIP-APPI.…”

“…It has been successfully applied to various samples such as Chinese drugs [11] and plasticizers [12]. Also quantification, which is still challenging with other types of ambient ion sources, is possible with this ion source as shown for coumarin in different cinnamon samples [13]. Additionally, extractive electrospray ionization (EESI) has been added to this ion source [14], which enables the detection of polar compounds without changing the ion source.…”