First synthesis, characterization, and evidence for the presence of hydroxycinnamic acid sulfate and glucuronide conjugates in human biological fluids as a result of coffee consumption.

A systematic investigation of the human metabolism of hydroxycinnamic acid conjugates was carried out. A set of 24 potential human metabolites of coffee polyphenols has been chemically prepared, and used as analytical standards for unequivocal identifications. These included glucuronide conjugates and sulfate esters of caffeic, ferulic, isoferulic, m-coumaric and p-coumaric acids as well as their dihydro derivatives. A particular focus has been made on caffeic and 3,4-dihydroxyphenylpropionic acid derivatives, especially the sulfate conjugates, for which regioselective preparation was particularly challenging, and have so far never been identified as human metabolites. Ten out of the 24 synthesized conjugates have been identified in human plasma and/or urine after coffee consumption. A number of these conjugates were synthesized, characterized and detected as hydroxycinnamic acid metabolites for the first time. This was the case of dihydroisoferulic acid 3'-O-glucuronide, caffeic acid 3'-sulfate, as well as the sulfate and glucuronide derivatives of 3,4-dihydroxyphenylpropionic acid.

Identification of ethyl formate as a quality marker of the fermented off-note in coffee by a nontargeted chemometric approach.

The quality of coffee is influenced by many factors such as coffee variety, agricultural and postharvest conditions, roasting parameters, and brewing. The pleasure of drinking coffee may be affected by off-notes such as burnt, green, earthy, or fermented. Their presence is related to the variety, fermentation during postharvest processing, or over-roasting of the beans. Sensory expert panels trained for the evaluation of coffee are able to detect off-notes and select coffees by well-defined quality criteria. The application of instrumental approaches detecting quality markers related to the perceived off-notes is shown to be useful to assist sensory panels. This paper describes the discovery of a new marker compound related to the fermented off-note occasionally perceived in coffees. The application of untargeted chemometric methods on volatile compounds revealed correlations between individual compounds and the sensory attribute. The new marker compound was identified as ethyl formate, which can be measured in the headspace of roasted and ground coffee by various analytical techniques including online proton transfer reaction mass spectrometry.