Analysis of pentacyclic triterpenes by LC–MS. A comparative study between APCI and APPI

Abstract

The analytical performances of three atmospheric‐pressure sources, electrospray (ESI), atmospheric‐pressure chemical ionization (APCI), and atmospheric‐pressure photoionization (APPI), were evaluated for the analysis of pentacyclic triterpenes in liquid chromatography–mass spectrometry (LC–MS). Among these sources, APPI and APCI are particularly well adapted to sensitive analyses of pentacyclic triterpenes by LC–MS. Detection parameters were optimized for both the sources, and the effects of three dopants (toluene, acetone and anisole) on the detection (sensitivity and ion fingerprints in MS spectra) were studied in detail for APPI–MS. The limits of quantification were measured under selected ion monitoring conditions, in the range of 0.005–0.015 mg l⁻¹ and 0.002–0.84 mg l⁻¹ in APPI and APCI, respectively, depending on the studied pentacyclic triterpene. Overall, APPI was found more sensitive than APCI in positive ion mode, whereas APCI shows the greatest sensitivity for acidic triterpenes in negative ion mode. Following this study, the developed LC–MS method was used for the characterization of pentacyclic triterpenes in three plant extracts. High amounts of betulinic acid, betulinic aldehyde and betulinic aldehyde acetate were observed in plane bark. The main component of birch bark is betulin and extracts of okoume resin exhibit high amounts of α‐ and β‐amyrin. Copyright © 2008 John Wiley & Sons, Ltd.