Exploring the formation of heterodimers of barley hydroxycinnamoylagmatines by oxidative enzymes.

ABSTRACT

Dimers of hydroxycinnamoylagmatines are phenolic compounds found in barley and beer. Although they are bioactive and sensory-active compounds, systematic reports on their structure-property relationships are missing. This is partly due to lack of protocols to obtain a diverse set of hydroxycinnamoylagmatine homo- and heterodimers. To better understand dimer formation in complex systems, combinations of the monomers coumaroylagmatine (CouAgm), feruloylagmatine (FerAgm), and sinapoylagmatine (SinAgm) were incubated with horseradish peroxidase. For all combinations, the main oxidative coupling products were homodimers. Additionally, minor amounts of heterodimers were formed, except for the combination of FerAgm and CouAgm. Oxidative coupling was also performed with laccases from Agaricus bisporus and Trametes versicolor, resulting in formation of the same coupling products and no formation of CouAgm-FerAgm heterodimers. Our protocol for oxidative coupling combinations of hydroxycinnamoylagmatines yielded a structurally diverse set of coupling products, facilitating production of dimers for future research on their structure-property relationships.