MicD-F and ArtGox act in tandem to install thiazoline and thiazole
backbones within globular proteins. (A) Cartoons illustrating the
sequences of RopC, RopM, and RopN and the conditions used for MicD-F-catalyzed
cyclodehydration (left arrow) or tandem cyclodehydration/dehydrogenation
catalyzed by MicD-F and ArtGox (right arrow). (B) Wavelength-dependent
circular dichroism spectra of RopC, RopM, and RopN at [monomer] =
20 μM in 10 mM phosphate, 100 mM NaCl, 150 μM TCEP, pH
7.0 and 25 °C. (C) LC/MS analysis of the reaction of RopC, RopN,
and RopM with MicD-F under the conditions shown in panel (A) above.
The characteristic loss of 18 mass units upon cyclodehydration is
evident for both RopC and RopM; the reaction of RopM was incomplete
under these conditions. (D) Treatment of RopC with MicD-F and ArtGox
under the conditions shown in panel (A) above led to clean conversion
into the corresponding thiazole (RopC-Z). (E) The wavelength-dependent
CD spectra of RopC-U and RopC-Z compared to RopC; these data are not
corrected for contributions due to the thiazoline or thiazole linkage.
(F) The melting temperatures of RopC, RopC-U, and RopC-Z (after refolding)
are almost identical.