Investigating CmlA specificity for alternate PCP domains.
(A) Sequence
alignments of PCP domains from chloramphenicol biosynthesis with PCP
domains accepted as CmlA substrates (from the teicoplanin and kistamicin
NRPS module 6) and those not accepted by CmlA (from the skyllamycin
NRPS modules 7 and 10). Predicated PCP secondary structure is shown,
with the degree of homology highlighted in yellow (similar), orange
(highly similar), and pink (identical). The post-translationally modified
serine residue (green asterisk) and residues implicated in the PCP-acceptance
in skyllamycin biosynthesis (blue squares) are indicated. A structural
model of PCP6tei demonstrates the location of similar residues
on the structure of such a PCP domain (colors as previously indicated).
(B–G) LCMS analysis of the reconstitution of hexapeptide extension
using separated M5 modules from teicoplanin biosynthesis with hybrid
module 6 constructs combining the A-domain from teicoplanin biosynthesis
together with PCP domains from the NRPS machinery from kistamicin
biosynthesis (module 6, B/E) and skyllamycin biosynthesis (module
7, C/F; module 10, D/G). Peptide biosynthesis was reconstituted with
either Bht (upper panels) or Tyr + CmlA (lower panels). Solid lines
indicate methylamide peptides (PCP-bound), and dashed lines indicate
hydrolyzed peptides (pentapeptide, black line; Bht-containing hexapeptide,
pink line).