(A) Proposed adducts
between CBXs and oligopeptides (UP1, CGKGCGSGYGW; UP2, AGKGCGSGYGW), i.e., irreversible
thiazoline with N-terminal Cys and reversible thioimidate with internal
Cys. UP1 adducts with monolabeled internal residues were
not detected. (B) UHPLC chromatograms at 280 nm for the Cys treatment
experiment with compound 52. Oligopeptides were incubated
with the compound for 30 min at 37 °C; then, Cys was added and
incubated for another 30 min. Full chromatograms are provided in the Supporting Information, Figure S21 and Oligopeptide Labeling. (C) Correlation between k2 with Cys (Figure 5) and conversion of UP2 oligopeptide
without the N-terminal Cys.