New Taste-Active 3-( O-β-d-Glucosyl)-2-oxoindole-3-acetic Acids and Diarylheptanoids in Cimiciato-Infected Hazelnuts.

Activity-guided fractionation in combination with sensory analytics, LC-TOF-MS, and 1D/2D-NMR spectroscopy enabled the identification of the bitter tasting diarylheptanoids asadanin, giffonin P, and the previously not reported ( E)-7,9,10,13-tetrahydroxy-1,7-bis(2-hydroxyphenyl)hept-9-en-11-one and 4,12,16-trihydroxy-2-oxatricyclo[13.3.1.13,7 ]-nonadeca-1(18),3,5,7(20),8,15,17-heptaen as well as the yet unknown astringent compounds 2-(3-hydroxy-2-oxoindolin-3-yl) acetic acid 3- O-6'-galactopyranosyl-2″-(2″oxoindolin-3″yl) acetate and 3-( O-β-d-glycosyl) dioxindole-3-acetic acid in Cimiciato-infected hazelnuts exhibiting a bitter off-taste. Quantitative LC-MS/MS studies, followed by dose/activity considerations confirmed for the first time asadanin to be the key contributor to the bitter taste of Cimiciato-infected hazelnuts. Furthermore, quantitative studies demonstrated that neither the physical damage alone nor a general microbial infection is able to initiate a stress-induced asadanin generation, but most likely either specific Cimiciato-specific microorganisms associated with the bugs or specific chemical stimulants in the bugs' saliva is the cause triggering asadanin biosynthesis. Finally, also germination was found for the first time to activate diarylheptanoid biosynthesis, resulting in higher contents of bitter tasting phytochemicals and development of the bitter off-taste.