Poly-γ-glutamic
acid (PGA) is a promising polymer that comprises d- and l-glutamic acid (Glu) connected via an amide bond. PGA is biosynthesized
by a transmembrane enzyme complex composed of PgsB, PgsC, and PgsA.
However, the detailed reaction, especially the mechanism for introducing d-Glu residues into PGA, remains elusive. We herein report isotope
tracer experiments with deuterated l- and d-Glu
and demonstrate that epimerization of a growing peptide is involved
in PGA biosynthesis.