Efficient Analysis of 2‑Acetyl-1-pyrroline in Foods Using a Novel Derivatization Strategy and LC-MS/MS

2-Acetyl-1-pyrroline (2-AP) is a key odorant in many foods, such as aromatic rice and wheat bread, with a very low odor threshold of 0.05 μg/L in water. The small molecule with a popcornlike, roasty odor is generated biologically or by Strecker degradation within the Maillard-reaction cascades during thermal food processing with methylglyoxal and 1-pyrroline as the main direct precursors. Numerous gas-chromatographic methods for the analysis of 2-AP have been published, but the reactivity of the compound leads to discrimination or degradation during sample workup. We developed a novel derivatization method for 2-AP with o-phenylenediamine followed by HPLC-MS/MS analysis of the resulting stable quinoxaline. The precision (7%), repeatability (14%), recovery (92%), linearity (0.79–500 μg/kg), limit of detection (LOD, 0.26 μg/kg), and limit of quantitation (LOQ, 0.79 μg/kg) were validated for rice matrix and were excellent as compared with those of methods published before. With the novel method, 2-AP levels in typical foods like aromatic rice (131 μg/kg), wheat bread (18 μg/kg), brown bread (18 μg/kg), rye bread (18 μg/kg), and popcorn (38 μg/kg) were determined.