Children of Nature: Thoughts on Targeted and Untargeted Analytical Approaches to Decipher Polyphenol Reactivity in Food Processing and Metabolism.

Following 25 years of polyphenol research in our laboratory, the astonishing chemical and metabolic reactivity of polyphenols resulting in considerable chemical diversity has emerged as the most remarkable attribute of this class of natural products. To illustrate this concept, we will present selected data from black tea and coffee chemistry. In black tea chemistry, enzymatic fermentation converts six catechin derivatives into an estimated 30 000 different polyphenolic compounds via a process we have termed the oxidative cascade process. In coffee roasting, around 45 chlorogenic acids are converted into an estimated 250 novel derivatives following a series of diverse chemical transformations. Following ingestion by humans, these dietary polyphenols, whether genuine secondary metabolites or food processing products, encounter the microorganisms of the gut microbiota, converting them into a myriad of novel structures. In the case of coffee, only two out of 250 chlorogenic acids are absorbed intact, with most others being subject to gut microbial metabolism. Modern mass spectrometry (MS) has been key in unravelling the true complexity of polyphenols subjected to food processing and metabolism. We will accompany this assay with a short overview on analytical strategies developed, including ultrahigh-resolution MS, tandem MS, multivariate statistics, and molecular networking that allow an insight into the fascinating chemical processes surrounding dietary polyphenols. Finally, experimental results studying biological activity of polyphenols will be presented and discussed, highlighting a general promiscuity of this class of compounds associated with nonselective protein binding leading to loss of enzymatic function, another noteworthy general property of many dietary polyphenols frequently overlooked.