The high-resolution molecular portrait of coffee: A gateway to insights into its roasting chemistry and comprehensive authenticity profiles.

The direct-infusion of 130 coffee samples into a Fourier-transform ion cyclotron mass spectrometer (FT-ICR-MS) provided an ultra-high resolution perspective on the molecular complexity of coffee: The exceptional resolving power and mass accuracy (± 0.2 ppm) facilitated the annotation of unambiguous molecular formulas to 11,500 mass signals. Utilizing this molecular diversity, we extracted hundreds of compound signals linked to the roasting process through guided Orthogonal Partial Least Squares (OPLS) analysis. Visualizations such as van Krevelen diagrams and Kendrick mass defect analysis provided deeper insights into the intrinsic compositional nature of these compounds and the complex chemistry underlying coffee roasting. Predictive OPLS-DA models established universal molecular profiles for rapid authentication of Coffea arabica versus Coffea canephora (Robusta) coffees. Compositional analysis revealed Robusta specific signals, indicative of tryptophan-conjugates of hydroxycinnamic acids. Complementary LC-ToF-MS confirmed their compound class, building blocks and structures. Their water-soluble nature allows for application across raw and roasted beans, as well as in ready-made coffee products.