Recognition
of a PKS module by its upstream ACP partner. Protein
interactions were detected by cross-linking either DEBS module 3 (A–C)
or module 3 + TE (D–F) to a modified form of its upstream ACP
partner from DEBS module 2. Synthesis of crypto-ACP2
is described in the Supporting Information. crypto-ACP2 (250 μM) was incubated with
module 3 or module 3 + TE (50 μM) in the absence (A, D) or presence
(B, E) of 10 mM diketide 1 (shown in Figure 2), which acylates the KS active
site of module 3 or module 3 + TE. The lower protein band in each
SDS–PAGE image corresponds to module 3 (160 kDa) or module
3 + TE (186 kDa), whereas the upper band corresponds to the cross-linked
adduct between the crypto-ACP and module 3 (181 kDa)
or module 3 + TE (207 kDa). In panels C and F, the crypto-ACP (250 μM) was incubated with module 3 or module 3 + TE
(50 μM) that had been preincubated with diketide 1 plus methylmalonyl-CoA thus enabling elongation of the diketide
chain. Chain elongation was initiated by addition of methylmalonyl-CoA,
and allowed to proceed for 1 min with either module. Whereas the absence
of cross-linking in panel C indicates generation of a closed turnstile
in module 3 following chain elongation (as represented by the “X”
over the KS active site thiol), the appearance of a cross-linked adduct
in panel F indicates that TE-catalyzed hydrolysis of the elongation
product allows the reopening of the turnstile.