MALDI-TOF-MS analysis of MjMcrA 11-mer peptide
thioamidation and MjMcrA–Y(+1)C 11-mer cyclodehydration.
The sequences of the McrA 11-mer variants with the site for thioamidation
(Gly(0)) in red, and the Cys(+1) replacement in blue. (A) Thioamidation
catalyzed by MjYcaO. Top: mass spectrum of the unmodified MjMcrA 11-mer peptide, m/z 1346.6 Da. Bottom: mass spectrum of the MjMcrA
11-mer peptide after reacting with MjYcaO, Na2S, and ATP, showing the thioamidated product, m/z 1362.6 Da. (B) Cyclodehydration catalyzed by MjYcaO. From top to bottom: mass spectrum of the unmodified MjMcrA–Y(+1)C 11-mer peptide; MjMcrA–Y(+1)C 11-mer treated with MjYcaO and ATP in the presence
of phosphate; acid hydrolysis of cyclodehydrated MjMcrA–Y(+1)C 11-mer peptide in [18O]-labeled water;
control where MjYcaO is omitted. (C) View of the MjYcaO (in cyan) bound to MjMcrA (shown
as tan sticks). The site of nucleophilic attack by the sulfur source
is shown with a purple arrow. (D) Superposition of the computational
structure of PatD (green) and TruD crystal structure (purple) with
the MjMcrA 11-mer peptide structure (shown as tan
sticks) modeled in the active site. In the peptide, Tyr(+1) has been
modified to a Ser for presentation.