As a PLP-dependent enzyme, the ACCD’s ringopening
reaction starts with a transformation reaction from an
internal aldimine between the PLP and the enzyme to an
external aldimine. In most of the PLP-dependent enzymes, the
next step is the nucleophilic abstraction of the a-substituent,
either an a-proton or a carboxylate group, to form an a-carbanionic
intermediate. This reaction mechanism cannot be applied
to ACCD because the substrate (ACC) does not contain a-hydrogen
and the carboxyl group is retained in the product.
Therefore, the ring-opening reaction of ACC must be initiated
without obvious accessibility to an a-carbanionic intermediate,
which is, for PLP-dependent enzymes, the common entry for
catalysis. One proposed reaction mechanism is the nucleophilic
addition to Cg followed by the cleavage of the Ca-Cg bond and
b-proton abstraction. Because PLP acts as an electron sink,
external aldimine is fairly electrophilic, and the nucleophilic
addition to Cg to rupture the