Generative Algorithm for Molecular Graphs Uncovers Products of Oil Oxidation

The autoxidation
of triglyceride (or triacylglycerol, TAG) is a
poorly understood complex system. It is known from mass spectrometry
measurements that, although initiated by a single molecule, this system
involves an abundance of intermediate species and a complex network
of reactions. For this reason, the attribution of the mass peaks to
exact molecular structures is difficult without additional information
about the system. We provide such information using a graph theory-based
algorithm. Our algorithm performs an automatic discovery of the chemical
reaction network that is responsible for the complexity of the mass
spectra in drying oils. This knowledge is then applied to match experimentally
measured mass spectra with computationally predicted molecular graphs.
We demonstrate this methodology on the autoxidation of triolein as
measured by electrospray ionization-mass spectrometry (ESI-MS). Our
protocol can be readily applied to investigate other oils and their
mixtures.